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By Reuben B. Ellestad, Fremont F. Clarke

Lithium chemical plant extraction methods are discussed with reference to 1) base exchange with alkali sulphates; 2) processing based on roasting with lime; 3) miscellaneous methods; and 4) application of the Lithium Corp. process to extraction of lithium from run-of-mine, low grade spodumene ore, or concentrates. IN the early days of the lithium industry most of the production was from lepidolite, zinnwaldite, and amblygonite. Nearly all the early extraction processes described in the literature involve heating the finely ground mineral with sulphuric or hydrochloric acid. On subsequent water leaching most of the bases present in the mineral (especially aluminum) are dissolved as sulphates. As a result, the leach solution required extensive chemical purification before the lithium could be precipitated as carbonate. Following the remarkable growth of the lithium industry to its present size, zinnwaldite and amblygonite ores must be considered of minor importance only. Attention is now focused on spodumene, abundant enough in North America to be a major source of supply, and there are important supplies of lepidolite and petalite in Africa. The extraction processes described below all apply to spodumene, although several will also operate on other lithium minerals, such as petalite. Base Exchange with Alkali Sulphates: A distinct advance was made with the disclosures of Wadman and von Girsewalt. In these methods the finely ground silicate ore (spodumene or lepidolite) is intimately mixed with an excess of alkali sulphate (usually K2SO4) in at least a 1 to 1 proportion, and the mixture was heated to a relatively high temperature. Base exchange results, with the formation of lithium sulphate. A water leach dissolves the lithium sulphate, together with the excess potassium sulphate. Successful operation of this type of process requires very thorough grinding and mixing, as well as careful temperature control. The use of K2SO4 is objectionable from cost considerations since purification of lithium carbonate requires the use of potassium carbonate, if the K2SO4 is to be recovered and recycled. The lower solubility of K2SO4 as compared with Na2S04 is also objectionable, since it limits the concentration of the Li2SO4 solution to be precipitated by K2SO4. Early laboratory-scale investigation of this process by Lithium Corp. was not encouraging. Other related base exchange processes are those of Lindblad, Wallden, and Sivander3 and Sivander, Gard, Villestad, and Wallen4. The former covers the reaction of lithium silicate minerals with a sodium sulphate solution, at 100" to 300°C (under pressure), while the latter involves the extraction of silicate minerals with molten sodium sulphate. Both these processes would seem to be difficult and expensive to operate.

Jan 1, 1956

By David R. Mitchell, B. M. Bird

DENSE-MEDIA processes utilize the familiar laboratory float-and-sink procedure on a commercial scale. Just as wood chips float on water and sand sinks, so coal floats and refuse sinks when placed in a medium intermediate in specific gravity between the coal and refuse. Liquids intermediate in specific gravity between coal and refuse used in commercial plants are of four types: (1) organic liquids of high specific gravity-halogenated hydrocarbons; (2) dissolved salts in water; (3) pseudo liquids obtained by suspending solids, such as sand or magnetite, in water, and, (4) fluidizing a mass of sand or other solids by air currents. Those most widely used for cleaning coal are solutions of calcium chloride in water and a suspended sand or magnetite pseudo liquid. Laboratory float-and-sink testing is an intermittent operation during which every opportunity is given for particles lighter than the medium to float and particles heavier to sink. Commercial processes are continuous; vertical and horizontal currents of the separating medium occur as either part of the process or unavoidedly produced by the introduction of feed and withdrawal of products, 'so that the exact separation of the laboratory technique is not duplicated by commercial processes. However, separations close to the theoretical are obtained in commercial machines by careful technical control of the process. Most machines in commercial installations are crowded to get as much out of the equipment as possible, so that careful technical control is necessary is get the recoveries and grade of product desired. Sizes usually cleaned are plus ¼ in. or plus 1/8 -in. in the United States and plus 1/16-in. in Great Britain. Coal as small as 1 mm. has been cleaned in some experimental installations. The separation of coal from refuse in sizes finer than about 1/8-in. is made difficult by viscosity effects and hence at the present time cleaning is confined to the coarser sizes. Technical advances in the art of cleaning coal by dense-media processes is progressing rapidly and it is likely that equipment, media, and procedures will be developed to clean sizes down to 0.5 mm. efficiently and at low cost.

Jan 1, 1950

By F. Lynwood Garrison

Except in the old Catalan forge, or its modifications, attempts to make iron and steel directly from ore in a practical and economical manner have failed so frequently and completely that such schemes are looked upon with justifiable distrust. Without exception, all have failed from one cause or another, although in some instances every indication of a practical success was manifest in the beginning. It is, therefore, necessary to carefully examine and consider every detail affecting the process, or more properly, furnace, under consideration. This I have done to the best of my ability during a long visit to Russia last summer, and after satisfactorily observing the practical success of the furnace in the iron works of Count Stroganoff at Dobriansky in the Government of Perm, I decided to investigate as completely as possible the history of similar furnaces in Finland and Russia. These data, sifted and verified with the greatest possible care, form the substance of the present paper.* An illustration on page 321 of Percy's Iron and Steel shows the old type of Osmundssmide or harkugnar, which has been in use in Northern Europe since pagan times. Fig. 1 shows a furnace of this kind. It should, perhaps, more properly be called a high-bloomary furnace or forge, the Swedish word hark meaning bloom or loupe. It was with this type of furnace that Mr. Husgafvel began his experiments at Porsaskoski in 1875. Attempts to obtain better results with larger furnaces of this type were failures, as every bloom or loupe obtained necessitated blowing out the furnace with a consequent large waste of fuel. A larger furnace of course increased this waste with no corresponding advantage. A movable hearth of threeeighth inch iron, lined with a mixture of clay, quartz and lime, was next tried, but in consequence of the frequent repairs of this lining,

Jan 1, 1888

Jan 1, 1904

By A. F. Colombo, R. T. Sorensen, D. W. Frommer

An analytical method has been developed and used in batch and continuous tests to provide initial insights into the effect of soluble calcium ion in anionic flotation of silica from iron ores. A deficiency or excess of calcium ion in pulps subjected to this type of flotation produces an impairment in flotation efficiency. Data developed in the investigation are from a single ore, but show that total calcium requirement is met from water, ore and reagent sources. In batch studies, starch additions were shown to exert no influence on the calcium level, but fatty acid and sodium hydroxide had subtractive effects. The investigation was next extended to continuous flotation testing where the general observations from batch testing were confirmed. Factorially designed experiments were performed showing that the relationship of calcium additions to flotation response was not a simple one, but tended to shift to higher additions with increased fatty acid. Nevertheless, the range of soluble calcium levels measured remained fairly constant in areas of good flotation response. It is concluded that techniques developed should be useful in removing empiricism from flotation operations in this and other systems requiring activation for success. Further development should aid in process control both through methods outlined and through investigations aimed at studying the effects of other soluble reagents. Of the major mineral commodities, iron ore was one of the last to succumb to flotation processing. Commenting on this fact, one of the speakers 1 at the convention celebrating the 50th Anniversary of flotation in the U.S.A., said ". . . in 1951 froth flotation as a means of beneficiating nonferrous minerals was a might giant and could be characterized by 'you name it, we float' - but not iron ore". This tardiness in applying flotation to iron ores was the result of a number of factors, including economics and ready availability of direct shipping ores. Even now, when the need for beneficiation can no longer be denied, proposals for flotation of iron ores are apt to be viewed with some misgivings. This disquiet results from knowledge that wide variability, which would necessitate corresponding adjustments in reagents, often exist within even a single ore deposit. Coupled with ore variability is the fact that, at present, there is no way of quickly and precisely anticipating the direction and magnitude of reagent changes required for uninterrupted production of acceptable concentrates. Despite the long delay, iron ore flotation is now practiced commercially, although the chief applications2-4 are to specular hematites having relatively coarse liberation and low slime content. In addition, the application of flotation in upgrading magnetic concentrates seems assured. However, these flotation methods do not appear applicable to substantial tonnages of fine grained, earthy, and frequently more complex semitaconites and nonmagnetic taconites. The U.S. Bureau of Mines, in devoting its attention to the semitaconite and nonmagnetic taconite class of materials, has demonstrated that anionic flotation of calcium-activated silica can be utilized with an expected high frequency of success.' Even so, it has been recognized that the flotation method is a complex one, and that the reagent suite must be carefully tailored to the feed. These conditions would be expected to offer difficulties in treating ores with the wide range of variability previously discussed. Accordingly, research was initiated to develop methods to remove much of the empiricism from the flotation operation by measuring the reagent variables within the pulp for a correlation with flotation response. A simple illustration of the technique sought would be in the well established use of pH meters to provide feedback control to reagent feeders and thereby limit acidity or alkalinity to a range producing optimum results. The first efforts in this area have been concerned with measurements of soluble calcium ion. Bureau experience in both laboratory and pilot plant over the past five years has proved that the amount of calcium

Jan 1, 1965

By Paul M. Tyler

Mineral raw materials, because they are essential to our industrial prosperity and military strength, must be made available in substantial quantities. regardless of cost. Variations in the cost of procuring minerals, as compared with the cost of obtaining other commodities, and changes in the cost of production of different minerals relative to one another, will naturally influence the quantities of a given mineral item that can be marketed readily. However, in the last analysis, the cost of winning minerals from the ground usually constitutes only a small fraction of the value of the end-use products and services derived from them. The miner's share of the cost of a typewriter, telephone circuit, or even a modem office building, is almost insignificant. Far more important to the ultimate consumer, therefore, than any minor saving in cost is the assurance of ample supplies of the minerals needed to aliment our expanding economy. To create a successful metal mining operation involves ( 1 ) the discovery and systematic development of a mineral deposit, (2) extraction of the ore, (3) the mechanical and metallurgical processing to eliminate worth- less or harmful impurities, and (4) the profitable disposal of the product. The first step of the technological process belongs chiefly in the realm of the geologist, the second is a mining engineer's job, the third is mainly up to the millmen and extractive metallurgists; whereas the fourth and equally important step poses a commercial problem that has aspects in common with the marketing of other products. Ore finding is far from being an exact science. There is no mathematical criterion for evaluating the efficiency of prospecting and exploration. Lady Luck shares the honors or assumes part of the blame along with the prospector and geologist. Marketing like- wise involves factors that seemingly defy engineering analysis. Although the other steps can be measured with some degree of mathematical accuracy, even they tend to vary so widely in basic principle, as well as in

Jan 1, 1959

By A. Matsubara

Jan 1, 1922

By A. Matsubara

Jan 1, 1922

By W. A. Eardley

FIFTEEN years ago the world's deepest oil well penetrated the earth about 7300 ft. That depth has now been more than doubled. Why has such deep drilling become necessary and how has it become possible? Three factors have had an important bearing: (1) Depletion of shallow zones, making it necessary to search for deeper producing measures. (2) The perfection of prospecting methods, which have been success- fully used to locate favorable buried structures, many at great depth. (3) Improvement in the quality of steels used for drilling.

Jan 1, 1940

By Clyde E. Williams

MODERN steelmaking has gradually evolved from an inefficient small-scale operation, utilizing tiny units, to a highly efficient one utilizing large units almost completely mechanized. The leading position of the United States in the steel industry is due to the possession of easily assembled high-grade raw materials and large-scale highly developed plants. Modern integrated steel operation is largely one of material handling. Mining and transportation of iron ore, coal, and fluxes, coking the coal in by-product ovens, smelting the ore with coke and limestone in blast furnaces, converting the resulting pig iron into steel in the Bessemer, or in the open hearth when supplemented with scrap, and fabricating the resulting steel ingots in the shapes of commerce all are done on a huge scale, mostly by machinery, most of the labor being employed either in operating the machine or keeping it in repair. At the same time the quality and uniformity of the product have been greatly increased by the development of scientific knowledge and operating skills. Thus, the steel industry in this country is highly developed both mechanically and technically.

Jan 1, 1942

By M. R. Tek, K. H. Coats, D. L. Katz

A large number of boundary value problems encountcred in unsteady-state heat transfer, fluid flow through porous media, neutron diffusion and mass transfer involve the solution of a linear, parabolic partial differential equation commonly refcrred to as the diffusivity equation, where U is the dependent potential variable. K is the diffusivity (hydraulic, thermal, neutron, etc.) and 1 is the time variablc. Solutions to Eq. I are available in the literature for a wide variety of initial and houndary conditions. The great majority of these solutions are ohtained for geometric boundaries corresponding to linear. cylindrical or spherical flow models. A typical engineering application where the solution to Eq. 1 is required is the calculation of underground water encroachment across the boundaries of oil or natural gas reservoirs, In this particular area of application, the reservoir boundary is invariably approximated by circular geometry. However. the areal shape of many reservoirs can be better approximated by elliptic rather than circular boundaries. Thus the need for a general method of solving the diffusivity equation in elliptic coordinates arises in this problem as well as in other engineering applications involving elliptic boundaries. The solution to the diffusivity equation usually in volves the Error Function for the linear flow model, Bessel functions for the radial flow model and trigonometric or Legendre functions for the spherical flow model. It is well known that the general solution to the diffusivity equation in elliptic coordinates involves Mathieu functions. The significance of Mathieu functions in the analytical treatment of the diffusivity equation in elliptic coordinates is discussed in the literature However, these references do not providc analytical solutions useful in practical engineering problems. The objectives of this papcr are the development of the equations describing the unsteady-state liquid flow through a porous medium with an elliptic inner boun- dary, the development of a numerical method of solving these equations and, finally, a comparison of the water encroachment quantities calculated from the elliptic flow equation with those calculated from the radial flow equation. While the specific problem treated in this paper relates to unsteady-state liquid flow through a porous medium, the basic equations and computational techniques devcloped will apply equally well to problems occurring in the other areas of engincering interest mentioned previously. The solution given here is limited to a single case in which thc outer boundary encloses an area 100 times that of the inner boundary. DESCRIPTION OF THE FLOW MODEL Fig. 1 shows the flow model upon which the calcu lations presented in this paper are based. The inncr and outer houndaries of the flow model are represented by two confocal ellipses with major and minor axes, respectively, equal to 2a1, 2b1, and 2a, and 26,. The height of the elliptic cylinder flow model is denoted by 17. The following assumptions are employed in the development 01 the equations governing the unsteady-state liquid flow through the described flow model. 1. Uniform porosity and permeability throughout the flow model

By C. E. Lesher

Two processes for agglomerating fine sized ores with low temperature coke are described. One process (Orcarb) agglomerates ores with limited amounts of carbon; the other (ore-carbon pellets) pelletizes fine sized ores, using low temperature cokes as the binder. Data are presented on the products obtained when taconite, magnetite, and hematite concentrates and several titanium oxide ores were used. REDUCTION of finely divided oxide ores has long been a major metallurgical problem. Various methods of agglomerating, notably briquetting, sintering, nodulizing, and pelletizing, have been developed and are in industrial use. Carbon is the usual reducing agent for oxide ores and attempts have been made to agglomerate fine ores with coking coal in order to get the metallurgical advantages of intimate contact and increased particle sizes suitable for subsequent smelting or reduction.1-3 For the past three years, research has been in progress on two processes for combining fine sized ores with reactive carbon in the form of low temperature coke. By one process, designated Orcarb, the ore is coated with coke carbon in amounts limited to that required for reduction and the result is an appreciable but limited increase in product particle size over that of the original ore. The second process, called ore-carbon pellets, produces pellets of fine ore bound by low temperature coke. The first objective was to develop a process for combining an oxide ore with only enough carbon for its reduction, the amount being that derived from the simple reduction equations. The carbon (that amount theoretically required for the reduction of the oxides in an agglomerate with ore), calculated to CO, ranges from 10 pct for zinc calcines or phosphate ores to 21 pct for rutile and 26 pct for silica. The carbon required for reducing iron oxides falls between the extremes—10 and 26 pct. When the carbon in the agglomerate is low temperature coke, reduction by hydrogen may be expected to take place, thus modifying the calculated carbon require- ment. On the other hand, in practice, an excess of reducing agent over that required in theory is normally used. Screen sizes of three iron ores on which the greater part of the experimental work was performed are given in Table I. Most of the testing was done with Freeport (Renton Mine) coal, but Pittsburgh and Elkhorn bed coals were also used. The first objective was to agglomerate the ore with sufficient low temperature coke to provide carbon for reduction, i.e., in the range from 10 to 25 pct. This was accomplished by preheating the ore, mixing with pulverized coking coal, and completing the coal carbonization in a plain steel rotating retort. The pilot retort, as it is now constituted, is shown by diagram in Fig. 1 and photograph, Fig. 2. Ore is fed into the upper kiln by a screw; it is heated to 900" to 1100°F by direct flame and it is then discharged into an insulating hopper from which it goes

Jan 1, 1956

By CHARLES SIMENSTAD

COAL preparation, or coal washing, is not a new subject to the Pacific Northwest. Most of the coals mined in this state smaller than lump, and nearly all such sizes mined on the Pacific slope of the Cascade mountains, require washing before marketing. A large proportion is being put through some washing process, but coal washing in this state, has not reached the efficiency it is practicable to obtain. In fields where the coal, as mined, contains less impurities, where working conditions make it practicable to eliminate some of these impurities under- ground, or where a large proportion of the run-of-mine coal is lump, coal preparation does not present the problem it does in our local field. Here the coal is associated with considerable impurities and the slack, or steam sizes, aggregate about 80 per cent. of the output. Therefore, approximately 80 per cent. of the coal mined must be washed to become a valuable fuel. Washing then becomes a major operation, as hand picking of the 20 per cent. of lump is a standard and comparatively simple operation. Some coal beds here are so interstratified with bone, of a more or less massive nature, that hand picking of lump is not economically efficient. In such cases the coal must be crushed fine enough for it to be freed from the bone, so that the two may be separated. Coal cleaning in this field, therefore, must receive skilled attention to purify this fuel and raise its stand- ard. Without greater efficiency in cleaning, the importation of coal from outside the state will be even greater than in the past.

Jan 1, 1926

By W. C. Maurer

Although millions of feet of rock are drilled annually, the basic drilling mechanisms involved are not well understood. The primary reason for this lack of knowledge is because the basic principles of rock failure are not well understood and rock failure is the primary mechanism in drilling. A better understanding of the drilling mechanisms would enable a more scientific approach to the design and use of drills and bits. The paper reviews several models which have been proposed to explain various aspects of the different drilling methods. These models are described and their limitations and areas of application are discussed. Drilling rate relationships are developed and related to the basic rock failure mechanisms. TYPES OF MECHANICAL DRILLS There are three basic methods of mechanically attacking rock: 1) percussive action, 2) rotary action, and 3) combined rotary-percussive action. A percussion drill applies a force perpendicular to the rock surface and the bit moves into the rock perpendicular to the surface, forming a crater beneath it (Fig. 1). A rotary drill applies a constant thrust to the bit while a torsional force moves the bit parallel to the rock surface, breaking the rock ahead of it. A rotary-percussive drill applies both a rotary force and a percussive force to the bit which moves into the rock at an angle to the surface. The commonly used drills can be classified as: rotary-drag, diamond; percussive-hammer, piston, churn; and combination-rotary-percussive, roller.

Jan 1, 1967

By C. H. Snyder

Tlie paper deals with details of construction of the Colmol, including improvements in design that will be incorporated in new models. These improvements are results of problems encountered and worked out in experimental operation with the unit. Also included is a descriptive plan of operating where roof and air conditions are of the worst. A summary of production results from the machine is presented. THE various units used in conventional mining are well-built. Generally the universal under -cutter, driven by approximately 50 hp, weighs approximately 25,000 lb, and is a very strong piece of machinery. The drilling machine is not as husky as an undercutter, generally is driven by approximately 15 hp, weighs about 9000 lb, but is a well-constructed, sturdy mechanism. The loader, usually 60 hp, weighs approximately 24,000 lb, and certainly is a strong, rugged unit. The working parts of all three of these sturdy conventional units have been made of tough steel alloys for some time. With the use of three machines having a combined horsepower of approximately 125, with a combined weight of approximately 60,000 lb, and with the possible inherent advantage of single purpose machines performing a single function, the use of considerable explosives has been required to complete the conventional mining cycle. It was therefore our thought, upon conception of the first Colmol,* a machine which was to do the work accomplished by the three conventional units plus explosives, that it must be a rugged mechanism. Now, after building several units, after going through many and varied experiments, and after the expense of some million-odd dollars, we find we have observed and learned nothing that contradicts our original thinking. A continuous miner, if it is to give satisfactory performance, must be a rugged piece of machinery. Ruggedness has been, and is constantly, in the minds of our engineers in designing the Colmol. Improvements where they have been required have been in the direction of more weight, more horse power, better alloys, bigger hydraulic pumps and motors; in short, always, toward more torque, greater strength, more ruggedness. Now not only the finest steel alloys are utilized but more than 100 Timken roller bearings are used. The following is some pertinent data on models being built and to be built: The low unit: Cutting height, 30 to 42 in. By changing the upper gear case the maximum cutting height can be increased to 61 in., giving a variable cutting height of from 30 to 61 in. Width of cut, 9 ft 6 in. Width of body, 75 in. over tracks. Height of body, 271/2 in. Overall length, 23 ft. Driven by three 50-hp motors or a total of 150 hp. Weight, 26 tons. The intermediate unit: Cutting height, 451/2 to 72 in. Width of cut, 9 ft 8 in. Width of body, 77 in. over tracks. Height of body, 43 in. Overall length, 26 ft. Driven by three 70-hp motors or a total of 210 hp. Weight, 35 tons.

Jan 1, 1951

By C. H. Snyder

Tlie paper deals with details of construction of the Colmol, including improvements in design that will be incorporated in new models. These improvements are results of problems encountered and worked out in experimental operation with the unit. Also included is a descriptive plan of operating where roof and air conditions are of the worst. A summary of production results from the machine is presented. THE various units used in conventional mining are well-built. Generally the universal under -cutter, driven by approximately 50 hp, weighs approximately 25,000 lb, and is a very strong piece of machinery. The drilling machine is not as husky as an undercutter, generally is driven by approximately 15 hp, weighs about 9000 lb, but is a well-constructed, sturdy mechanism. The loader, usually 60 hp, weighs approximately 24,000 lb, and certainly is a strong, rugged unit. The working parts of all three of these sturdy conventional units have been made of tough steel alloys for some time. With the use of three machines having a combined horsepower of approximately 125, with a combined weight of approximately 60,000 lb, and with the possible inherent advantage of single purpose machines performing a single function, the use of considerable explosives has been required to complete the conventional mining cycle. It was therefore our thought, upon conception of the first Colmol,* a machine which was to do the work accomplished by the three conventional units plus explosives, that it must be a rugged mechanism. Now, after building several units, after going through many and varied experiments, and after the expense of some million-odd dollars, we find we have observed and learned nothing that contradicts our original thinking. A continuous miner, if it is to give satisfactory performance, must be a rugged piece of machinery. Ruggedness has been, and is constantly, in the minds of our engineers in designing the Colmol. Improvements where they have been required have been in the direction of more weight, more horse power, better alloys, bigger hydraulic pumps and motors; in short, always, toward more torque, greater strength, more ruggedness. Now not only the finest steel alloys are utilized but more than 100 Timken roller bearings are used. The following is some pertinent data on models being built and to be built: The low unit: Cutting height, 30 to 42 in. By changing the upper gear case the maximum cutting height can be increased to 61 in., giving a variable cutting height of from 30 to 61 in. Width of cut, 9 ft 6 in. Width of body, 75 in. over tracks. Height of body, 271/2 in. Overall length, 23 ft. Driven by three 50-hp motors or a total of 150 hp. Weight, 26 tons. The intermediate unit: Cutting height, 451/2 to 72 in. Width of cut, 9 ft 8 in. Width of body, 77 in. over tracks. Height of body, 43 in. Overall length, 26 ft. Driven by three 70-hp motors or a total of 210 hp. Weight, 35 tons.

Jan 1, 1951

By M. E. Hassan, J. C. Calhoun, R. F. Nielson

An apparatus was constructed for the measurement of inter-facial tensions over a range of temperatures and pressures. This apparatus utilized the pendent drop method, and resembles in construction similar apparatus recently described in the literature and in use in some petroleum research laboratories. The interfacial tensions of benzene, propane, n-pentane, n-hexane. n-octane. and iso-octane against water were measured at temperatures ranging from 26" to 82" C and at pressures ranging from 1 to 204 atm. Values of interfacial tensions for the henzene-water system and their variations with temperature and pressure are generally in good agreement with value? of previous investigations. The data in all cases showed a slight decrease of interfacial tension with pressure at constant temperature in the range studied. The effect of pressure became less as the pressure was increased, with an indication of a reversal of the effect at higher pressures. There was a decrease of interfacial tension with temperature at constant pressure in all cases, as would normally be expected. This rate of decrease became greater the higher the temperature. A general equation is presented for the interfacial tensions as a function of presPurp and temperature over the range studied, and the constants calculated for each system. A definite trend was found in the effect of molecular weight on the interfacial tension at a given temperature and pressure, for the homologous series from propane to n-octane. Data for n-decane from the literature fitted well into this trend. INTRODUCTION It has been recognized for many years that surface forces play an active part in the production history of an oil reservoir as well as in determining the amount of unrecoverable oil. The magnitudes of these forces are governed by the values of the interfacial tensions. These vary greatly with composition, pressure, and temperature. The effect of composition is greater than that of pressure and temperature over the ranges normally encountered. In fact, because of the variety of compounds present in a crude, no attempt has yet been made to correlate crude composition with its surface tension or with its interfacial tension against water. The amount of dissolved methane greatly affects the surface properties of an oil, and there are "surface-active" compounds in crudes which have a much greater effect on boundary tensions than do equal amounts of hydrocarbons. The purpose of the present work was partly to contribute data that would eventually be used in correlations applicable

Jan 1, 1953

By C. R. Knopp

Gas-oil relative permeability ratio is an important relationship in oil reservoir predictive calculations. A correlation has been developed from 107 gas-flood k/k tests on Venezuelan core samples. The correlating parameter is based on restored-state water saturation tests and' is applicable to both consolidated and poorly consolidated sandstone reservoirs. Data of the correlation show that there are no distinguishah1e differences between the mass-data groupings for the two c1assifications A procedure is recommended for running .sufficient relative. permeability analyses to compute a geometric mean of the sample group. The geometric mean is more representative of the total core, and probably the entire reservoir. For example, while only one in four of the k,,/k,., test curves agreed closely with the resultant correlation of this report, the geometric mean curves of the 16 suites (three samples or more). showed good agreetment ill three cases out of four. INTRODUCTION The gas-oil relative permeability ratio is an important, fundamental relationship in most oil reservoir predictive calculations. Predictive calculations are made to estimate future reservoir production characteristics and ultimate oil recovery. The k1,/k2, relationship is specifically needed to relate the surface gas-oil ratio to the reservoir oil and gas saturation, and to calculate the relative movement of these phases within the reservoir whenever some of the more complex driving mechanisms are present. Laboratory k1/k2, tests are not generally run as a routine analysis. Consequently, k1/k2 data often are not available when needed because the cost of laboratory work could not be justified or the need for such data had not been properly anticipated. When laboratory k1/k2, data are available, they are often very difficult to interpret. For example, wide divergence is sometimes shown in a family of k1,/k1, tests representative of the producing horizon in a single well. With these considerations in mind, a study was made to determine if a relationship might exist between the k1,/k2, curve and some other simple laboratory test criteria. The most probable k1/k2, curve correlation for Venezuela described in this paper is the result of the investigation. The presented correlation defines the most probable gas-flood k,,/k,, curve through the medium of air-water capillary displacement and centrifuge water saturation tests. The laboratory procedures of these tests are. relatively simple, and inexpensive; test data should be. widely available- from routine analysis. DATA AVAILABLE, LABORATORY METHODS The report correlation utilized 107 gas-Hood k1/k2, tests run on sandstone cores of Venezuelan reservoirs. Table 1 is a general tabulation of data pertinent to the tests, while Table 2 summarizes the data. Thetests include 96 from Western Venezuela and 11 from Eastern Venezuela. Eighty-two- of the 107 test samples were sandstones that varied from poorly consolidated to-unconsolidated; 25 were consolidated. The average sample porosity was 26.7 per cent and the average permeability was 1,121 md; these values typify the better sandstone reservoirs of' Venezuela. The Welge gas-flood technique,' based on fundamental Buckley-Leverett frontal displacement theory, was introduced in about 1952 and is widely accepted in the industry. The laboratory procedure is relatively simple, rapid, and can be performed on small core samples. While there have been some minor variations in sample preparation and laboratory procedure in the tests used for the correlation, these tests can be generally summarized as follows. The core sample was first sol vent-extracted and dried. Connate-water saturation was restored by the oil-flushing or evaporation-blow down methods. At the beginning of gas flood the hydrocarbon pore volume was completeiy saturated with the test oil phase. Unsteady-state gas-oil displacement then began with the injection of nitrogen or helium. while the displaced oil and gas phases were incrementally metered at the out-flow face. From the test data, the k,,/k,, curve was calculated by the Welge method.' The individual oil and gas relative permeabilities were also calculated." CORRELATING PROCEDURES In attempting to establish a basis of correlation, we found that broad mid-range sections of 105 of the 107 k,,/k,, test curves could be closely duplicated by a straight line. Only two curves did not show a degree of linearity in this region. Correlation-curve definition parameters were subsequently developed from this observation of consistent mid-range linearity. Possible correlating variables were limited to the physical properties measured on core samples that (1) were widely available as common test data and (2) could be easily and cheaply obtained through future laboratory work. The more obvious possibilities were porosity, permeability and

Jan 1, 1966

By R. F. Domagala, M. Hansen, D. J. McPherson

Iodide zirconium was combined with calculated amounts of nitrided zirconium sponge and arc melted to prepare alloys in the 0 to 6 wt pct N region. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat-treated specimens permitted construction of the binary phase diagram from 0 to 6 pct N. Features of the diagram include the peritectic formation of both a and ß solid solutions. The maximum solubility of nitrogen is 0.8 pct in 8 zirconium and 4.8 pct in a zirconium. An X-ray study of nitrided materials was made in the range 6 to 13 wt pct N region because serious nitrogen losses were experienced when attempts were made to arc melt these high nitrogen alloys. PHASE relationships in the Zr-N system have been determined. Due to the inability to retain nitrogen in nitrogen-rich alloys subjected to arc melting, definitive work was possible only in the range 0 to 6 wt pct (0 to 30 atomic pct) N. Sufficient complementary X-ray work was done to permit construction of the binary phase diagram up to 13.3 wt pct (50 atomic pct) N (ZrN). Small ingots were prepared by arc melting master alloys with enough zirconium to produce an alloy of the desired composition. Following pretreatment, alloys were annealed at temperature levels between 600" and 2020°C. Determination of the phase boundaries was then accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to corroborate solidus curves, and X-ray diffraction was employed to study the nitrogen-rich region of the a + ZrN phase field. Materials Westinghouse Grade 1 iodide zirconium crystal bar served as the base material for this investigation. The as-received bars were lightly sandblasted, pickled in a 20 pct HN0-5 pct HF aqueous solution, rinsed in water and acetone, and dried. They were rolled to about 1/32 in. strip and acid-pickled, followed by water and then acetone rinses. The material was sheared to approximately 1/4 in. squares, cleaned with acetone, and stored for use. Pure zirconium nitride is not commercially available, according to correspondence with possible suppliers. A literature survey indicated that nitrogen may be introduced into zirconium metal by passing nitrogen or ammonia gas over zirconium at an elevated temperature. After considerable experimentation, a train was devised whereby high quality nitrogen was passed through a series of bubblers to remove the last traces of oxygen, through an H,SO, bubbler and a cold trap to remove moisture, and finally over zirconium within a resistance furnace. Hand-picked Bureau of Mines magnesium-reduced zirconium sponge proved more amenable to nitriding than the crystal bar. The nitrogen used was extra pure gas purchased from Linde Air Products Co. The first two bubblers through which the gas was passed contained a solution suggested by L. F. Fieser" as being ideal for removing the last traces of oxygen from nitrogen. The solution contains 20 g KOH, 2 g sodium-anthraquinone ,9-sulphonate, and 15 g NaHSO, dissolved in 100 ml water. It is blood-red and turns brown when contaminated with oxygen. A saturated lead acetate solution, next in the series of bubblers, removed any H2S which might have formed in the 0, removal stage. An H,SO, bubbler and cold trap removed moisture before the nitrogen was passed over the zirconium. The zirconium was contained in a stainless steel screen within a Vycor or quartz tube in a resistance furnace. Unreacted nitrogen passed out of the system through a mercury bubbler. A nitriding run was performed in the following manner: Zirconium was placed in the screen within the furnace tube. The unit was assembled, suitably clamped off, and evacuated to remove the air and moisture within the tube and that trapped by the zirconium sponge. The unit was flushed with nitrogen and evacuated twice. After nitrogen was allowed to pass over the zirconium for about 30 min, the furnace was turned on; several hours were required to reach temperature. The reaction was allowed to continue at temperature for about 4 hr and the screen was then withdrawn from the hot zone of the furnace by means of a Nichrome or Kanthal rod. The screen and its contents were allowed to cool at the end of the tube and were then removed. At 800°C no more than about 5 pct N could be introduced into the sponge zirconium. This material was designated M-1 (master alloy No. 1) and reserved for the preparation of alloys in the dilute nitrogen region. A second set of experiments was conducted at 1000°C; no more than 7.2 pct N could be introduced into the zirconium at this temperature. Enough material (M-2) of this nitrogen content was prepared to produce a second set of alloys to complement the first and to provide alloys in the 0 to 6 wt pct N range. It was hoped that a diffusion anneal plus a re-nitriding might yield a material of higher nitrogen content. The material containing about 7 pct N was therefore given a homogenization treatment at 1000°C for 6 hr under an argon atmosphere. It was

Jan 1, 1957

J. T. LITTLETON, JR., ? Corning, N. Y. (written discussion?).-This. discussion will add little that has not been brought out but will show how the problems encountered in the Corning Glass Works were overcome. The chief points of consideration in any equipment are, first, the work the equipment is called upon to do; second, the installation; and, third, the man who will use it. These three points should determine the type of apparatus adopted. If only rough measurements, merely a little better than the eye, are desired, the cost of the instruments should be considered; but if accurate temperature control is necessary, the cost of the equipment deserves only small consideration. There is no question that the real problem for any factory is the installation, making sure that the elements really give the temperatures desired; also, the instruments must be so designed that any man can use them.

Jan 12, 1919