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By F. W. Schremp, J. W. Chittum, T. S. Arczynski

This paper describes a laboratory study of causes of external casing corrosion and the test work that led to the use of oxygen scavengers to prevent this attack. External casing failures are classified as water-line, casing-casing, collar and body failures. A corrosion mechanism based on principles of differential oxygen availability is developed that is consistent with facts known about each kind of failure. The field use of oxygen scavengers is depicted as a direct result of the laboratory study. A part of the paper is devoted to reporting on the field use of hydra-zine to control external casing corrosion. Results of field measurements made over a period of several years are presented as evidence of the efectiveness of the hydrazine treatment. The first conclusion reached is that the use of hydrazine materially reduces the cathodic protection requirements for treated wells. This result is interpreted to mean that a reduction is taking place in the amount of corrosion on the casing. Results indicate also that hydrazine shows its greatest usefulness within the first 12 to 18 months after a well is completed when pitting corrosion is likely to be most active. INTRODUCTION According to surveys sponsored by the National Association of Corrosion Engineers,' the cost of repairing casing leaks caused by external corrosion may exceed $4 million per year. In addition, well damage and lost production resulting from casing leaks probably costs the petroleum industry an additional $5 to $6 million per year. Concern about the cost of external casing corrosion led to an extensive laboratory study of factors causing this external corrosion and to the development of a new approach to its prevention. This paper presents a discussion of various causes of external casing corrosion, details of laboratory studies and the results of the field use of an oxygen scavenger in well cementing fluids to prevent the external corrosion of oil-string casing. Measurements on test wells over a period of several years show that cathodic-protection current requirements are greatly reduced when hydrazine is used in cementing mud. Reduction of current requirements can be interpreted to mean that removal of oxygen by hydrazine has greatly suppressed corrosion cells on the external surface of the casing and thereby, has reduced corrosion. To date, hydrazine has been used by the Standard Oil Co. of California in more than 200 well completions. KINDS OF CASING FAILURES A survey of a large number of casing leaks disclosed four types of external casing failures — water-line, casing-casing, collar and body failures. These types are identified largely by their location on the casing. Water-line failures are found just below the surface of water or mud in the casing annulus. Casing-casing failures occur on the oil string just below the shoe of the surface string. Collar failures are found in the threaded ends of casing joints where they are screwed into casing collars. Body failures may occur at any point on the body of a casing joint. Ex- amples of each kind of failure have some of the general characteristics that are shown in Fig. 1. Water-line failures usually result in the circumferential severance of an oil-string casing. The corrosive action causing a water-line failure usually is sharply defined and is limited to a short length of the casing. Casing-casing failures usually are accompanied by pitting corrosion distributed around the oil-string casing for distances up to 100-ft below the shoe of the surface string. Casing-casing failures may also sever the casing. Collar failures seem to start on the first thread at the bottom of recesses between collar and casing joint. Corrosion proceeds across the threads by what appears to be a normal pitting mechanism. Both casing and collar are severely attacked. Body failures are the result of highly localized pitting at any point on a casing wall. Besides the pit that perforates a casing, a large number of other pits usually are found along one side of the casing joint. The pits occasionally are filled with corrosion products consisting largely of oxides and sulfides.' Frequently, the mill scale is largely intact on the rest of the casing. Examination of a casing failure does not always reveal the cause of the failure. Frequently, the necessary details are destroyed when the failure occurs. For example, formation water flowing through a perforation at high velocity may enlarge the hole and destroy any remaining evidence of the cause of the failure. One way to obtain undistorted information about a failure is to study the nature of other pits on the casing in the vicinity of the failure. A study of such pits frequently suggests that they are characteristic of an attack resulting from the differential availability of molecular oxygen.

By Charles W. Tandy, Wm. I. Weisman

Sodium sulfate is an important industrial chemical, being one of perhaps a dozen or so chemical commodities that are produced and consumed in the United States in quantities exceeding one million short tons per year. In recent years over half of the country's production of sodium sulfate has come from natural sources, whereas 20 years ago only 25% was derived from these sources. Production of natural sodium sulfate from various types of deposits is the main source of this chemical in Canada and Mexico, and probably in Argentina, Chile, and the USSR. [Table 1] illustrates the growth in production of natural sodium sulfate in the United States. Mineralogy and Physical Properties Sodium sulfate is widespread in occurrence and is a common constituent of many mineral waters, as well as seawater. Many of the saline or alkali lakes throughout the world contain varying amounts of sodium sulfate. In its natural form it is found as the hydrous salt, mirabilite, commonly called Glauber's salt, and as thenardite, the anhydrous variety. The largest quantities occur in the form of mirabilite. Sodium sulfate is found in varying degrees of purity, from theoretically pure efflorescent crystals of mirabilite to combinations and admixtures of other salts and impurities. It is a common constituent of some brines, and it is from this source that much is extracted commercially. Sodium sulfate is also found combined with other compounds, such as the mineral glauberite, the double salt of anhydrous sodium and calcium sulfate, and blödite, the double salt of sodium sulfate and magnesium sulfate. While these and other minerals containing sodium sulfate are not economically important, they are of interest because of their frequent occurrence. The reader is referred to other publications (Cole, 1926; Dana, 1932; Grabau, 1920) for descriptions of these minerals. Only the two economically important minerals, mirabilite and thenardite, will be described herein. Mirabilite, Na2SO4 • 10H2O, contains 55.9% water of crystallization. It is noted for its efflorescence or spontaneous loss of water. On

Jan 1, 1975

By J. S. Marsh

AN incomplete statistical analysis performed wearily on the morning after Thursday, Feb. 12, indicates that the unavoidable items of conversation among steelmen were the current shortage of sleeping time and the "Normandie." No analysis is needed, however, to be certain that many thousands of valuable words were uttered, both in and out of technical sessions, concerning matters of deep interest to members of the Iron and Steel Division. The opening session consisted mostly of papers that have appeared, or will appear shortly, in Metals Technology. One, however, that was not finished in time to be printed in any form, but that aroused great interest, was by E. L. Ramsey and L. G. Graper (Wisconsin Steel Works). Its subject was the production of high-sulphur steel by treatment with sulphur dioxide derived from anhydrous sodium sulphite or bisulphite added to the ladle or to the mold. The sulphide distribution in the finished steel is such that increased machinability and longer tool life result. Both items are of obvious importance in these days of mighty production.

Jan 1, 1942

By Howard N. Eavenson

In many of the bituminous-coal districts of this country, more than one seam of workable coal exists, and in most cases the lower seam is the more attractive, owing to either its greater thickness or its superior quality. Apprehension that the mining of a seam will destroy the availability of all overlying seams has hindered the development of many fields and has led to the unprofitable working of certain seams in order to save them from an expected total loss. The U. S. Coal & Coke Co., Gary, W. Va., was the first operator in the Pocahontas field to mine the No. 4 seam extensively, which occurs about 80 ft. above No. 3, the scam that was worked first. This was due to the fact that over large areas the upper seam was the only one of workable thickness, at that time. In two places, both seams were workable in the same area, the No. 4 being thinner and containing more impurities than No. 3 seam. In mining these areas, an attempt was made to keep the workings in the upper seam in advance of those in the lower one, and no pillar robbing was done in No. 3 seam until after pillars in that part of the upper seam directly over it had been mined. This resulted in an excessive development in the lower seam, with large areas of finished rooms and standing pillars. The top fell badly, and after a couple of years the falls became so heavy that pillar drawing was unduly expensive. To overcome this obstacle and allow No. 3 seam to be worked in some territory where No. 4 was thick, but too dirty for present use, a study was made of operating methods applied to superimposed seams in Pennsylvania and Maryland. This was started more than seven yean ago by the writer; his data, supplemented by more recent information gathered by his associates, and by two cases mentioned in recent foreign publications, form the basis of this paper. Central Pennsylvania In central Pennsylvania, the lower coal measures contain several seams of nearly the same thickness but of varying quality, and as mining

Jan 1, 1923

By Howard N. Eavenson

In many of the bituminous-coal districts of this country, more than one seam of workable coal exists, and in most cases the lower seam is the more attractive, owing to either its greater thickness or its superior quality. Apprehension that the mining of a seam will destroy the availability of all overlying seams has hindered the development of many fields and has led to the unprofitable working of certain seams in order to save them from an expected total loss. The U. S. Coal & Coke Co., Gary, W. Va., was the first operator in the Pocahontas field to mine the No. 4 seam extensively, which occurs about 80 ft. above No. 3, the scam that was worked first. This was due to the fact that over large areas the upper seam was the only one of workable thickness, at that time. In two places, both seams were workable in the same area, the No. 4 being thinner and containing more impurities than No. 3 seam. In mining these areas, an attempt was made to keep the workings in the upper seam in advance of those in the lower one, and no pillar robbing was done in No. 3 seam until after pillars in that part of the upper seam directly over it had been mined. This resulted in an excessive development in the lower seam, with large areas of finished rooms and standing pillars. The top fell badly, and after a couple of years the falls became so heavy that pillar drawing was unduly expensive. To overcome this obstacle and allow No. 3 seam to be worked in some territory where No. 4 was thick, but too dirty for present use, a study was made of operating methods applied to superimposed seams in Pennsylvania and Maryland. This was started more than seven yean ago by the writer; his data, supplemented by more recent information gathered by his associates, and by two cases mentioned in recent foreign publications, form the basis of this paper. Central Pennsylvania In central Pennsylvania, the lower coal measures contain several seams of nearly the same thickness but of varying quality, and as mining

Jan 1, 1923

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.' The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8'10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By Joseph L. Patrick

Geologic exploration, which has experienced an upward trend in the United States since 1962, continued with increasing activity through 1965. New, spectacular discoveries of recent years and continued questionable economic and political climates in many areas of the world have continued to focus the exploration attention of an increasing number of companies on the United States. Traditional geologic field methods are being bolstered by development of new methods, techniques and geophysical instruments. Reports from the states emphasize that successful exploration is dependent upon the combined effort of geochemistry, geophysics and geology, with high quality laboratory support of the field effort becoming increasingly necessary. PROGRAMS NOW UNDERWAY IN WEST During 1965 mineral exploration reached an all- time high in Nevada. Although examinations are being carried on throughout the State, much of the work is limited to two areas. The first area to attract recent exploration interest, initiated by discovery of the Carlin gold mine by Newmont Mining Corp., is an area of windows near the leading edge of the Roberts Mountains thrust fault in northeastern Nevada. Included in this area are the old camps of Mountain City, Battle Mountain, Cortez, Mineral Hill and Eureka. Major mining companies are using a combination of surface mapping, geochemistry, geophysics (largely induced potential surveys), following up with drilling. The second area of exploration is along the Walker Lane, a wide shear zone that parallels the Nevada-California boundary from Virginia City to Las Vegas. Activity has been intense in the Tonopah-Yerington area. Discovery of a large copper-iron deposit following an airborne magnetometer survey first focused recent attention on Walker Lane. Sixteen major companies are involved in exploration in the State.

Jan 2, 1966

By C. E. Webber

The economical recovery of the valuable constituents from the effluent of gas-con-densate wells has developed into a problem of balancing the cost of recovery against the cost of compressing the residual gas back into the formation. A possible method of extracting the gasoline and distillate from the natural gas is by oil absorption at high pressures. In order to design and evaluate an absorption plant, fundamental data on the composition of the coexisting hydro- carbon vapor and liquid phases at various temperatures and pressures are essential. A review of the literature indicated that the necessary data for the design of such plants are lacking. The nearest approach to desired published data is that of Katz and Hackmuth,~ who experimentally deter-mined the composition of the coexisting vapor and liquid phases in a natural gas-crude oil system at pressures up to 3000 lb. per sq. in. and at temperatures from 40' to zoo°F. This paper presents the results of the experimental determination of the equilib-rium distribution of the hydrocarbons methane through hexane between natural gas and a typical absorber oil. The ranges of temperature and pressure chosen were from 33' to r8oUF. and from 100 to 5000 lb. per sq. inch. Materials The absorber oil was a typical naturally occurring, Straw-colored distillate that had previously been steam-distilled to an initial boiling point of 300 F. The physical and chemical properties, including the results of an Engler distillation, are presented in Table I. A large volume of this oil was obtained and it was used throughout the complete set of experiments. Table i.—Properties of the Absorption Oil Gravity .......................... . . 32.5' A.P.1. Molecular weight by benzene freezing- point depression.................. 183 Viscosity, poises; at 100°F........... 0.0a80 At 200°F...................... 0.0102 Composition, PeR Cent Aromatics........ 24.0 Naphthenes..... 36.7 unsaturates,Aromatics...... .I24.00.3 1 Parafins Naphthenes.....36.7 39.o EngLeR Distillation Per Cent /ncg. F. Per Cent Dez. P. Initial boilins rmint.. 300 I 60....... 523 5.................. 402 I 70....... 538 10.................. 421 180....... 557 20.................. 462 90....... 570 30.................. 480 1 95....... 623 40.................. 49 .................1 511 Residue, z .o per cent; loss, 0.3 per cent. See refrence I. The n-hexane was obtained from the Ohio Chemical and Manufacturing Co., Cleveland, Ohio. This liquid had a boiling range of from 149" to 152.6'F., with a density of 0.667 at 60°F. and a molecular weight of 85 by benzene freezing-point depression. The propane, isobutane, wbu-tane, isopentane and n-pentane were ob-ta,ined from the Philgas Department of the Phillips Petroleum Co. Certified analyses of these compounds showed their purity to be in excess of 99.5 per cent and they were riot further purified.

Jan 1, 1941

By C. E. Webber

The economical recovery of the valuable constituents from the effluent of gas-con-densate wells has developed into a problem of balancing the cost of recovery against the cost of compressing the residual gas back into the formation. A possible method of extracting the gasoline and distillate from the natural gas is by oil absorption at high pressures. In order to design and evaluate an absorption plant, fundamental data on the composition of the coexisting hydro- carbon vapor and liquid phases at various temperatures and pressures are essential. A review of the literature indicated that the necessary data for the design of such plants are lacking. The nearest approach to desired published data is that of Katz and Hackmuth,~ who experimentally deter-mined the composition of the coexisting vapor and liquid phases in a natural gas-crude oil system at pressures up to 3000 lb. per sq. in. and at temperatures from 40' to zoo°F. This paper presents the results of the experimental determination of the equilib-rium distribution of the hydrocarbons methane through hexane between natural gas and a typical absorber oil. The ranges of temperature and pressure chosen were from 33' to r8oUF. and from 100 to 5000 lb. per sq. inch. Materials The absorber oil was a typical naturally occurring, Straw-colored distillate that had previously been steam-distilled to an initial boiling point of 300 F. The physical and chemical properties, including the results of an Engler distillation, are presented in Table I. A large volume of this oil was obtained and it was used throughout the complete set of experiments. Table i.—Properties of the Absorption Oil Gravity .......................... . . 32.5' A.P.1. Molecular weight by benzene freezing- point depression.................. 183 Viscosity, poises; at 100°F........... 0.0a80 At 200°F...................... 0.0102 Composition, PeR Cent Aromatics........ 24.0 Naphthenes..... 36.7 unsaturates,Aromatics...... .I24.00.3 1 Parafins Naphthenes.....36.7 39.o EngLeR Distillation Per Cent /ncg. F. Per Cent Dez. P. Initial boilins rmint.. 300 I 60....... 523 5.................. 402 I 70....... 538 10.................. 421 180....... 557 20.................. 462 90....... 570 30.................. 480 1 95....... 623 40.................. 49 .................1 511 Residue, z .o per cent; loss, 0.3 per cent. See refrence I. The n-hexane was obtained from the Ohio Chemical and Manufacturing Co., Cleveland, Ohio. This liquid had a boiling range of from 149" to 152.6'F., with a density of 0.667 at 60°F. and a molecular weight of 85 by benzene freezing-point depression. The propane, isobutane, wbu-tane, isopentane and n-pentane were ob-ta,ined from the Philgas Department of the Phillips Petroleum Co. Certified analyses of these compounds showed their purity to be in excess of 99.5 per cent and they were riot further purified.

Jan 1, 1941

By F. L. Toy, C. E. Sims

PNEUMATIC processes for converting molten pig iron to steel were the major producers of steel during the latter half of the 19th Century and until shortly after the turn of the century, when these processes began losing ground to their rival—the basic open hearth process. The first pneumatic process for converting molten pig iron to steel was introduced almost simultaneously by Sir Henry Bessemer in England and by William Kelley in the United States during the decade 1850-1860, but it was Bessemer who pushed it to a successful commercial operation. The process itself is so basically simple that it has not lent itself to many extensive or revolutionary improvements since its inception. During the first 30 yr, numerous' designs of vessel and many modifications of practice were tried before the industry standardized on something resembling current practice. The evolution in construction has resulted in proportions and arrangements based more on mechanical expedience than on metallurgical requirements. Many of the early converters were stationary and had to be tapped similarly to the cupola or open hearth furnace. Such types were used for many years in Sweden and Germany, but the rotating or tilting types were favored in England and the United States. There was evident trouble with bottom tuyeres, becAuse about half of the early designs were constructed for side blowing with tuyeres submerged below the metal-bath surface. Even portable tuyeres, introduced from above, were tried. The principal advance, which made bottom blowing practical, was the invention, in 1863, by Henry Bessemer, and subsequent improvement by A. L. Holley, of a detachable bottom so that the tuyere section could be renewed. In the meantime, it was the demonstration, by Robert Mushet, of the value of manganese in overcoming hot-shortness in converter steel, that made the process metallurgically feasible. At first, only the acid practice was used, and Swedish pig iron, because of its low sulphur and phosphorus, was in great demand. The development of a suitable basic lining, by Sidney G. Thomas and Percy G. Gilchrist in 1876-1879, made the process applicable to the high-phosphorus ores of Europe. From the beginning of the use of the Thomas-Gilchrist process, trouble was experienced in obtaining sufficiently high temperatures in the blown metal, particularly in small heats. It is necessary, of course, to have the low-carbon blown metal at a considerably higher temperature for handling from vessel to ladle to molds than is needed for the molten pig iron. All of the increase in temperature in a pneumatic process must be obtained from the heat of combustion of the elements contained in the pig iron plus that from silicon when ferrosilicon is added. In bottom blowing practice, carbon is almost completely burned, but inasmuch as it cannot be oxidized to a higher state of oxidation than to CO when in contact with liquid iron, only a minor portion of the heat-producing capacity is utilized. Under such conditions, it is not considered to be an efficient source of heat. In the acid practice, therefore, silicon and manganese are the large heat producers, are quickly oxidized, and are efficient fuels. Too much manganese, however, thins the slag greatly and tends to promote excessive slopping or throwing of slag and metal from the converter during the blow. Most operators, therefore, like to keep the manganese content of the iron below 0.60 pct, and thus the main source of heat is the silicon, which must be at least 1 pct and sometimes 2 to 3 pct for small blows such as for castings. Ferrosilicon is sometimes added during the blow to obtain an adequate temperature level. In the basic (Thomas) practice, even more heat is required, because cold lime is added to flux the phosphorus after it is oxidized, and the basic slag must be maintained at a proper temperature. Silicon

Jan 1, 1951

By F. B. Plummer

THE practice of introducing acid into oil wells to increase production of oil and gas has been in use since 1894, when it was first used in the Pennsylvania. oil fields30.? It is only since 1928 that it has been used to any extent in the Mid-Continent18. The process has proved successful in increasing production, at least temporarily, in depleted oil fields where the producing formation is highly calcareous and where water drive is not too pronounced. In the Zwolle field in Louisiana, where the producing horizon is a chalk, increases of 100 per cent have been recorded25. In north-central Texas, where the oil is produced from the Marble Falls limestone, equally pronounced increases have resulted3. The production also in some fields yielding oil from quartz sand cemented with calcite has been benefited. The evidence of actual increase in total recovery of oil, however, has been questioned by some engineers18. It has been pointed out that the results of the treatment of a well in a new district, where the process has never been tried out, can never be predicted with certainty, since other factors besides percentage of calcareous content: of the oil sand play a large part in determining the success of the method. Numerous articles have been published on acid treatment and on the effects of acid on limestone1-35, yet very little has been written con-cerning experimental work on the actual effect, of acid on capillary pores and larger oil-coated voids of oil sands. This is due partly to difficulties in duplicating field conditions in a laboratory and partly to the fact that the process has been carried out largely by contracting companies that have been unwilling to publish details of their results for fear of loss of business to competitors. The authors, using equipment developed to measure the radial permeability of oil-sand cores29, have developed a method of investigating the results of acid treatment which has enabled

Jan 1, 1935

By R. J. Wagner, G. H. Gronhovd, A. J. Wittmier

The paper describes the results of a series of full-scale boiler tests run to determine the ash fouling characteristics of a North Dakota lignite as a function of sodium content of the coal. Four levels of sodium were investigated and rate of fouling was determined both by boiler performance and by specially constructed probe equipment. Discussed is information on chemical and physical properties of the ash deposits. The vast lignite deposits in North Dakota are becoming increasingly important as a source of low-cost fuel for power generation. A new 200-megawatt lignite-burning plant located near Stanton, N.D., was placed in operation early in 1966. Another 172-mega-watt unit in the same area is scheduled for operation late in 1966, and plans have recently been announced for a 212-megawatt unit to be in operation by 1970. If these plants show good performance, western North Dakota could become a major power production center for a large geographic area in the upper midwest. One of the problems associated with the use of lignite in power boilers is its tendency to form troublesome ash deposits on boiler tube surfaces. This problem varies considerably from one lignite-fired boiler to another and is dependent upon such factors as source of lignite, boiler design, load factor, tube metal temperatures, and soot-blowing practices. This report presents data on sodium content* variation in a North Dakota mine, describes the results of a series of tests performed to determine the relationship between ash fouling tendencies and the sodium content, and tells how the mining company and electric utility have coordinated their operations to reduce the ash fouling problem. GENERAL BACKGROUND Until recent years it was generally assumed that North Dakota lignite from a given mine had qualities peculiar to that mine, but that within the mine, the lignite was quite uniform. In 1959, the Otter Tail Power Co. installed a 53.5-megawatt lignite-burning unit at its Hoot Lake plant, Fergus Falls, Minn. Shortly after the unit was put into operation, it was noted that at certain times under high load conditions, ash fouling problems were quite severe, but not consistent or predictable. Each time fouling occurred in the unit the position of the loading shovel at the mine was noted. Within two years it became apparent that there were certain areas in the Knife River Coal Mining Co. mine at Beulah, N.D., where the lignite apparently had a high fouling tendency for the Hoot Lake unit. Results from analyses of the coal did not show large differences in moisture percentage, ash percentage, heating value, or ash fusion temperature between the highly troublesome and less troublesome coals. After three years of operation, the troublesome areas had been quite well defined and the mining company started a procedure of bypassing these areas when load conditions at the plant were high and then returning to the troublesome areas to load the lignite during the summer months when peak loads were lower. It was noted that the lignite from the areas which caused severe fouling under high load conditions produced much less fouling at the lower summer loads. However, bypassing certain areas in the strip pit caused the mining company to disrupt their continuous loading schedule, which in turn upset their continuous stripping schedule and made for less efficient mining operation. Meanwhile, at the Hoot Lake plant, the number of soot blowers on No. 2 boiler had been increased from 30 to 55, and a very rigorous blowing schedule had been adopted resulting in soot blowers operating at least some part of 21 hrs per day. Fouling problems continued, with a resulting reduction in plant economy and reliability. During this period the Federal Bureau of Mines Coal Research Laboratory at Grand Forks, N.D., had initiated various research programs relating to the study of lignite ash and ash fouling problems. One project was a survey in which full seam samples were obtained from various locations in all the major

Jan 1, 1968

THE SOUTHWEST MINING SECTION of the National Safety. Council held a well attended two-day conference at Globe, Ariz., March 19 and 20; followed by two days of mine-rescue maneuvers at the Old Dominion mine in cooperation with the Globe-Miami District Mine Rescue and First Aid Association and the U. S. Bureau of Mines. C. L. Colburn of the Bureau had general charge of the arrangements and was chairman of the conference. All sessions were held in the Old Dominion Library. The program of papers was as follows: MINE FIRE PREVENTION AND FIGHTING What to do in Case of a Mine Fire. / Chas. A. Mitke, Consulting Mining Engineer, Bisbee, Ariz. Gunnite as a Fire Preventative. W. C. Browning, General Manager, Magma Copper Co., Superior, Ariz. Chemical Engineer's Part in Fire Fighting. Dr. L. H. Duschak, Consulting Chemical Engineer, San Francisco, Cal. Mine Fire Drills. A. C. Stoddard, Chief Mining Engineer, Inspiration Consolidated Copper Co., Inspiration, Ariz. Notes on the Installation of Fire Fighting Equipment in Mines. Benjamin F. Tillson, Assistant Superintendent, New Jersey Zinc Co., Franklin, N. J.

Jan 5, 1923

By George A. Yurko

The Cominco smelter, located at Trail, British Columbia, Canada, produces 180 000 metric tons of lead bullion annually in conventional blast furnaces. The resulting slag from these furnaces, 210 000 metric tons annually, containing 18 per cent zinc and 2.5 per cent lead, is treated directly in the slag fuming plant for the recovery of these metals and other valuable metals present in smaller quantities. Slag fuming is carried out on a 55 metric ton batch process in completely water-jacketed furnaces where the slag is blown with a mixture of powdered coal and air. The coal-to-air ratio is con- trolled to maintain strongly reducing conditions, thus, fuming the metals from the slag. The metal vapours are subsequently re-oxidized with air above the bath. The mixture of oxides is carried from the furnace by the gases through waste heat boilers and cooling flues to a baghouse where they are collected. The slag fuming plant, under normal conditions, will treat 700 metric tons of slag daily. The throughput in the plant is dependent on the fuming rate of zinc, which is a function of the composition of the slag, and on the economics, which dictate the extent to which zinc is fumed from the slag. Zinc and lead collected daily as fume average 113 metric tons and 17 metric tons, respectively, corresponding to recoveries of 89 per cent zinc and 98 per cent lead from the slag. The waste heat boilers produce 61 metric tons steam per hour, which is distributed to other processing plants.

Jan 1, 1970

By J. F. Myers, R. J. Tower

"THERE is nothing new under the sun." All over the world, mineral-dressing engineers are working at their problems, no two of which are alike. Each encounters equipment and process problems. Many devise simple ways and means of overcoming their difficulties. Many of these problems are quite common in the industry, yet, since no one human being seems capable of thinking of everything, these problems at some plants often are looked upon as necessary evils. The purpose of this symposium is to gather together, from competent engineers, devices and practices that have been useful to them. Most of the ideas contributed are not new, yet there is no plant operator, old timer or youngster, who will not find some idea herein that will give him a suggestion for improving his operation. Space does not permit a complete elaboration on all of the contributions offered. Each item is summarized, but this will be ample for those skilled in the art of mineral dressing. A list of contributors appears at the end of the paper, and the superior number at the end of each item identifies its source. GENERAL EQUIPMENT A signal light to show that a steel bin, containing relatively fine, moist ore, is full, can be made by suspending a copper rod in the bin to a sufficient depth to ensure ample contact with the ore. One wire of a 32-volt circuit should be attached to the rod and one to the side of the bin. Sufficient current will flow to make the signal light burn. A 110-volt circuit could be used, but 32 volts ensures safety.10 Fig I shows a circular bin for crushed ore. It is a concrete structure footed on the ground, using no supporting columns. Tailing from the sink-float was used for aggregate. Cross conveyors for discharging ore are not required, nor is a tripper for filling. Segregation is minimized by drawing from different gates. An exhaust fan on top of the bin eliminates condensation due to temperature of the ore.21 A beam with an adjustable point of suspension near the center permits rigging rolls for removal in a very few minutes. This makes unnecessary the lacing of the cable through the hub bolts on one side, around the shaft on the other, and the trouble of balancing the load.8 The ratchet handle on a Symons crusher may be replaced by a drum with a cable wound on it. When the cable is pulled by a crane or hoist it causes the drum to revolve and thus screws or unscrews the bowl. This reduces handwork and materially shortens the time required for the job.3 To spread ore feed from an apron feeder over a belt conveyor, place a heavy steel bar about midway between the top

Jan 1, 1947

By E. F. Bailey, L. S. Birks

The effect of stress on the austenite to ferrite transformation in carbon steel was studied by X-ray diffraction techniques. Tensile stress was found to cause reorienta-tion of austenite above the transformation temperature, to accelerate equilibrium conditions at the transformation temperature, and to cause precipitation of large carbides at a critical value of stress. IN the past, a number of papers' have discussed the effect of stress on the austenite to martensite transformation at relatively low temperatures. In general, it has been shown that tensile stress induces some transformation at a given temperature, while compressive stress retards the transformation. Very little work has been reported on the effect of stress on the transformation from austenite to ferrite plus carbide near the A, point in steel. One of the few papers in the literature2 reports an increase in A1 of about 1°C in pearlitic steel upon the application of tensile stress. In this paper, the effect of tensile stress on eutec-toid steel at, and above, the A, point was studied in

Jan 1, 1956

By P. Wynblatt, J. E. Dorn

The effect of strain rate, temperature, and interstitial impurity concentration on the flow stress was investigated in a poly crystalline Fe-2 pct Mn alloy. The temperature dependence of the flow stress was found to be independent of the interstitial impurity concentration, removal of interstitials merely decreasing the atherma1 stress level. Below 160%, the large temperature dependence of the flow stress was interpreted in terms of the Dorn-Rajnak theory of the Peierls mechanism of plastic deformation. Above 160"K, some other thermally activated intrinsic meckanisln seems to be operating. The strong temperature dependence of the flow stress of bcc iron at low temperatures has been studied by numerous investigators and interpreted in terms of several different thermally activated dislocation mechanisms. The following mechanisms have been proposed: a) interaction of dislocations with interstitial impurity atoms1 or with solute atoms in general; b) interaction of dislocations with clusters of impurity atoms;3 c) resistance to the motion of dislocations due to jogs on screw dislocations;* d) resistance to the motion of dislocations due to the Snoeck effect;' and e) interaction of dislocations with the intrinsic resistance of the bcc lattice or Peierls "hills". In previous work: it was found that the plastic behavior of polycrystalline iron containing 2 wt pct Mn (and 100 ppm C + N) is in good agreement with predictions based on the Peierls mechanismlo from 77" to 160°K whereas from 160" to about 370°K another as yet unidentified thermally activated mechanism is operative. The purpose of the present investigation was to determine the effect of interstitial impurities on the temperature dependence of the flow stress, by purifying the previously investigated alloy with respect to interstitial impurities. The investigation revealed that removal of the interstitial impurities to a level that eliminated Cottrell locking and the Portevin-LeChatelier effect (i.e., serrations in the stress-strain curve due to dynamic strain aging) affects neither the strong temperature dependence of the flow stress at low temperatures nor the general characteristics of the higher-temperature behavior. Such purification, however, lowered the athermal yield stress. I) EXPERIMENTAL PROCEDURE AND RESULTS The material used in this investigation consisted of an Fe-2 wt pct Mn alloy having the following additional elements present: 0.004 pct C, 0.006 pct N, 0.05 pct 0, 0.004 pct S, 0.003 pct P, and 0.001 pct Si. This was the same material as that studied in the previous investigation and will henceforth be referred to as the "impure material". The as received -jr by 2 in. hot-rolled bars were cold-rolled to 0.08-in. thickness, recrys-tallized under argon for 30 min at 80O0C, and further cold-rolled to 0.053-in. thickness. Flat tensile specimens 3 in. wide having a 1.625-in.-long gage section were machined from the sheet and then purified. The first stage of purification consisted of holding the specimens at 850°C for 24 hr in a stream of hydrogen saturated with water vapor at room temperature. Material prepared in this fashion will subsequently be referred to as "wet hydrogen purified material". It has been estimated that this type of treatment reduces the carbon content of iron to less than 5 ppm.' The second stage of purification consisted of holding the specimens in a closed system through which hydrogen was circulated past the heated specimens as well as a zirconium hydride getter. The specimens were held at 850°C and the getter at 800°C. The process was continued for 212 hr. The starting material for this process was wet hydrogen purified material. Material prepared in this manner will be referred to as "ZrHz purified material". The technique used was substantially the same as that described by Stein et al.' who have shown that the carbon level at the end of the process is reduced to about 5 parts per billion. The mean grain size of the three materials was found to be -60 C( for the impure material and -160p for the wet hydrogen and ZrHz purified materials. All tensile testing was carried out on an Instron Testing Machine either in controlled-temperature baths or at fixed-point baths such as boiling liquid nitrogen, and so forth. When fixed points were used the temperature was kept constant to better than *1°C whereas in all other tests the temperature variation was less than *2°C. Test of Purity. It was not possible to determine the purity achieved at each stage of the purification because the resulting level of interstitial impurities was near or below the limit of sensitivity of standard analytical techniques. It was possible, however, to obtain a qualitative measure of the extent of purification from the appearance of the stress-strain curves for the three materials. Fig. 1 shows the stress-strain curves for the three different materials tested at 300°K. It can be seen that the effect of wet hydrogen

Jan 1, 1967

By R. F. Slack, J. C. Draper, J. A. Younkins

In 1959, the Duquesne Light Co. was faced with the problem of moving more than 40 million tons of bituminous coal in Greene County, Pa. The coal had to travel a distance of about 4 ½ miles from a new mine portal in Rocky Run Valley to the company preparation plant and loading facilities on the Monongahela River. After careful study of this immense transport problem, Duquesne decided that the belt conveyor system described in the following pages offered the best solution. This system, now in operation, is probably one of the four or five longest permanent overland conveyor systems in existence. The general layout of the entire system is shown in Fig. I. A detailed description of the salient features of the system is presented below. THE MINE The valley of Rocky Run where the system begins is very, very narrow and very steep. It was chosen as the site of Duquesne's new mine portal because it was the only place on this particular property where the Sewickley coal seam cropped out. The valley also had two other advantages. First, it fronted on a state road and, second, it offered a site where some 4 million gallons of water could be stored for use in dust-allaying sprays needed in the mine. The company elected to construct a drift mine in the valley because this would require neither the hoisting time of a shaft mine nor the walking time of a slope mine. As part of the mine construction project, the valley was leveled by relocating its stream and filling its center with material cut from each side.

Jan 11, 1966

By S. R. Goodman, Hsun Hu, R. S. Cline

The quenching technique has been used to study phase relations in the composition area 2FeO.SiO2-FeO-SiO2-MnO.Si02-ZMnO.SiO2 of the system iron oxide-manganese oxide-silica under strongly reducing conditions such as exist in a gas mixture consisting of equul parts of carbon dioxide and hydrogen. Liquidus and solidus temperatures of most mixtures in the composition area studied are in the range of 1173° to 1345°C. EQUILIBRIUM relations existing among the oxides of iron, manganese, and silicon are of particular interest in two areas of steelmaking: slags and ingot inclusions. Mixtures of these oxides represent about 90 pct of the slag in the acid steelmaking process, and so dominate the chemistry of the whole refining process. These constituents also play an important role in the early slags existing at the time of the "lime boil" in the basic open hearth process. If these slags are liquid, they "wet" the lumps of lime rising from the bottom of the bath, and react with them. A liquid slag rich in CaO is then formed at the very beginning of the refining. Because the temperature is still low, all conditions for a good dephosphoriza-tion are fulfilled at this stage of the operation. Metal deoxidized with ferromanganese or silico-manganese is likely to contain, as inclusions, phases made up from among the oxides of iron, manganese, and silicon. A knowledge of stability relations existing among the phases present in this system, therefore, enables one to predict the hardness of the inclusions encountered. Moreover, because the shape of the inclusions in steel has a profound influence on the physical properties of the metal, it is important to establish whether or not the oxidic material is present as liquid or crystalline phases during heating and rolling of the steel (-1150 to 1350°C). A knowledge of melting relations in synthetic mixtures of iron oxide, manganese oxide, and silica will give a clue to these problems. Methods for determining such relations and the results obtained are described iln this paper. I) PREVIOUS WORK A number cf previous studies have dealt with the three "binary"* systems bounding the system iron oxide-mangar,.ese oxide-silica. The system iron oxide-silica was studied by Bowen and shairerl in 1932. Their data were obtained by equilibration of mixtures in contact with metallic iron. Phase relations for the system iron oxide-silica ill atmospheres of different oxygen pressures car1 be derived from data on the system FeO-Fe2O3-SiO2 as determined by Muan.2 The diagram shown iri Fig. l is a section of this system in an atmosphere of CO2 and H2 in ratio 1:l. The system manganese oxide-silica has also been the subject of several investigations. Most of the early studies suffered from a lack of proper control of the atmosphere under which the equilibrations were carried mt. Phase diagrams for the system at two well defined levels of oxygen pressures have been determined recently. Glasser3 determined stability relations in an atmosphere consisting of carbon dioxide and hydrogen in ratio 5:1, diagram Fig. 2, and Muan4 studied phase relations in the system in air.

Jan 1, 1962

By H. H. Kaveler, W. R. Evans, Jack Tarner

The geological features, development history and engineering detail of the Shuler Field and the results of approximately two years of unitized operation of the Shuler Jones Sand Pool, were discussed in a prior publication.' The purpose of this paper is to present the results of pressure maintenance in the Shuler Jones Sand Pool after nine years of unit operation. GENERAL INFORMATION The Shuler Jones Sand Pool is located in and about Section 18, Township 18 South, Range 17 West, Union County, Ark. The pool was discovered .in September, 1937, unitized in February, 1941, and subjected to gas injection operations in July, 1941. Water was first returned to the reservoir in July, 1944. The reservoir is an anticlinal trap covering about 4,000 acres. The 154,000 acre-ft of sandstone initially consisted of approximately 150,000 acre-ft of productive oil zone and 4,000 acre-ft of gas-cap. The average depth of production is 7,400 ft. Maximum closure of the reservoir is 135 ft and the oil column lies between a gas-oil contact at -7,270 ft and a water-oil contact at -7,370 to -7,380 ft. The field is approximately four miles long. east and .west, and one and one-half miles wide. The sand grains are angular and vary from fine to medium size. The porosity of the sandstone averages 20.2 per cent. The specific permeability averages 400 md. Some zones have as high as 30 per cent porosity and specific permeability of 4,000 md. The reservoir rock is not uniform in character but consists of sandstone zones interspersed with shale. The variation in rock characteristics is evident in the electric log and core analyses presented in the original publication. Asphalt present in the pore space of the sandstone limited the reservoir to the southeast and apparently blocked any encroachment of water from that direction. The initial reservoir pressure at a subsea depth of 7,300 ft was 3,520 psi. The reservoir temperature was 198ºF. Initially, the solution gas volume was 765 cu ft per bbl and the reservoir volume factor was 1.45. The gas solubility and formation-volume-factors of the reservoir liquid are related with reservoir pressures above 300 psi as follows: Solution gas, cu ft per cu ft, S = 0.0334 P + 18.65 Formation volume factor of reservoir oil, FVF = 8.0 x 10 -5 P + 1.168 Gas volume factor, standard cu ft of gas equivalent to one cu ft of gas at reservoir conditions of temperature and pressure, F = .062 P - 4 Pressure (P) measured in psia. The equation for the gas volume factor presented above is based on a direct measurement of a sample of the gas and is a correction of that used in the original paper. The gravity of the oil produced is from 32 to 34" API. CALCULATION OF INITIAL OIL IN PLACE The Jones Sand production history is interesting because it lends itself to analysis by material balance. Production statistics from discovery of the Jones Sand through 1949 and material balance calculations of the initial stock tank oil in place are shown in Table I. The usual procedure in testing the application of material balance calculations is to compute the apparent initial volume of oil in place, using production and pressure information obtained at different time periods. If the apparent oil in place volumes computed increase with successive time periods, water encroachment is indicated and approximations must be mads to correct for its influence. The first requirement in utilizing such calculations is reliable reservoir pressure, accumulated gas, oil and water production, and PVT data. Calculations of apparent oil in place in the Jones Pool, based on field data

Jan 1, 1951