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By G. G. Brown

Enthalpy-entropy diagrams are presented for natural gases of 0.6, 0.7, 0.8, 0.9, and 1.0 gravity over the pressure range of 5 to 10,000 Ib. per sq. in. and temperature range of 32º to 700°F. The charts indicate directly the work requirement and temperature rise for adiabatic compression or temperature change for free emansion of natural eases. Computation and Uses of Charts The Mollier diagram (Fig. 4), in which the enthalpy (heat content) is plotted against the entropy with lines of constant temperature, pressure,, and in some cases volume, has been found most convenient when dealing with the compression, expansion, and flow of fluids. In dealing with the flow of fluids, the sum of the increase in the enthalpy, AH, plus the increase in kinetic energy, AM —, plus the increase in potential energy, ?MZ, representing the total increase in energy of the fluid in flow, is equal to the sum of the heat q, and work added, —w, to the fluid while flowing between the entrance and exit of the flow system. AH + AM— + ?MZ = q-w [1] In cases where there is no significant change in potential energy or in kinetic energy (velocity), it follows that the increase in enthalpy is equal to the total energy supplied to the fluid. Under such conditions' the changes in the property of the fluid as it flows through a throttling valve, choke, or any other similar arrangement, may be read directly from the enthalpy-entropy diagram by following a horizolltal line between the known pressures' When compressing Or expanding a gas by means of a Or or engine in which no heat is added to or subtracted from the gas, but only work done, the changes in the properties of the gas may be determined along a vertical line of constant entropy between the entering and exit pressures. The power required for the compression of the gas may be readily determined by converting the increase in enthalpy into the desired units. The enthalpy-entropy diagram for natural gases is to the gas engineer what the steam diagram is to the steam-power engineer. For this reason it would be extremely convenient if a reasonably satisfactory enthalpy-entropy diagram could be prepared as a function of the gravity of the gas. A careful study of the known properties of natural gas indicate that this is possible. The effect of temperature upon the enthalpy at constant pressure is expressed as the "heat capacity" or "specific heat" of the gas. The best available data for natural and petroleum refinery gases indicates the relationship shown in Fig. I. From this it is clear that the specific heat of natural gases is a function only of the gas gravity and the temperature at atmospheric pressure. The effect of pressure on the enthalpy of natural gases is dependent upon the pressure-volume-temperature relationships,

Jan 1, 1945

By J. E. Campbell, G. D. Calkins, N. M. Ewbank, M. Pobereskin, A. Wesner

GRINDING for size reduction affects the economics of many processes and products. It is essential as the first step in many industrial processes and is also a finishing step for materials with properties depending on particle size, such as talc, cement, and silica sand. Intermediate and fine grinding are vital operations in the U. S. cement industry, which is producing more than 250 million bbl of cement per year.' Wear of the grinding media is a large part of the grinding operation cost. Problems encountered in grinding cement are so complex that evaluation of efficiency and economy of grinding media is difficult.2 It has been especially difficult to evaluate the relative effectiveness of different types of balls because there are no good testing techniques. Many other industrial operations can be evaluated on a laboratory scale with reasonable accuracy. This does not hold true for evaluation of grinding balls. The consistent results obtained in a laboratory test under a given set of conditions are not always borne out in field application. Rough evaluations of the effectiveness of various compositions and types of grinding balls have been made in the field by using a full charge of one type in a mill and comparing the production record with another run using another type of ball. This method is time-consuming and not very precise, as the second run may not have been carried out under identical conditions. Laboratory-scale tests, on the other hand, have yielded inconclusive results, and many investigators have turned their attention to the development of a field testing technique. Field testing small sample lots of grinding balls has been impractical because it is difficult to identify and recover the test specimens from the grinding mill, and individual groups of balls that have undergone different heat treatments can not be separated.".4 To overcome these difficulties, previous investigators have identified the balls by distinctive marks, notches, and drilled holes, but this procedure has three serious drawbacks: 1) Grinding characteristics and quality of the steel balls may be affected. 2) Physical markings may be worn away in the grinding process, especially during a prolonged run. 3) Recovery from the bulk of the charge will be extremely difficult because the markings are hard to see and may be masked by a coating of the product. To circumvent these difficulties, a radioactive-tracer technique was proposed for recovery and separation of steel grinding balls and subsequent evaluation of the various compositions of the balls. The proposed technique involved five basic operations: 1) Thermal-neutron irradiation activation5 of each group of test grinding balls to a different level of specific radioactivity. 2) Addition of groups of radioactive steel-ball specimens into a ball tube mill. 3) Recovery of radioactive steel-ball specimens from the bulk of the mill charge. 4) Separation of the various groups by their specific radioactivity. 5) Evaluation of actual grinding ball wear. Before any physical tests were performed, required neutron irradiation intensity and time were calculated. Probable composition of the steels to be used was ascertained. An examination was made of the radioactive nuclides8 to be formed which would contribute measurably to the radiation level immediately after irradiation and during the test operation. The radioisotopes formed, their types of radiation, and their half lives are listed in Table I. Of these radioisotopes only iron-59 and chromium-51 were significant for the actual wear test. The intensity of radiation that could be detected by a Geiger counter when the test was completed was the basis for the minimum activation level established. The intensity of radiaton that could be safely handled at the beginning of the test was the basis for the maximum activation level, although this was not considered a major problem. Ten groups of grinding balls of various composition and/or surface or heat treatment were to be tested. One group was designated for the minimum irradiation time. The remaining groups were designated for irradiation periods that increased by increments of 33 pct from that of each preceding group. This difference was considered enough for separation and identification of the groups by comparison of specific activity. Potential Hazards: Possible radiation hazards that might be encountered during this experiment were evaluated for the three important phases: 1) the radiation hazard of placing balls and removing them from the mill, 2) contamination of the product cement by radioactive material worn from the balls, and 3) contamination of the steel by the radioactive balls left in the mill. The radiation intensity expected from the whole group of radioactive balls was calculated to be 250 milliroentgen per hr at 1 ft. This meant the balls would require special shielded packaging and warning labels on the shipping containers. In a radiation field of 250 mr per hr a man can work for 1 hr without exceeding maximum permissible weekly exposure. Since the balls could be dumped into the mill in a matter of seconds, relatively little radiation exposure was anticipated at this stage of the operation. If the weight loss in the balls was 7.7 pct per month and the cement feed through the mill was

Jan 1, 1958

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

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

By Clinton L. Miller

MINING operations have been carried on in the immediate area of the Elizabeth mine during periods of high copper prices since 1793, when copperas and vermillion were first won from the outcrop. Present operations started in 1942 as a war baby. Since then production has totaled 1.7 million tons of 1.8 pct Cu ore. Elizabeth mining operations are on a pyrrhotite- chalcopyrite orebody contained in a gently plunging amphibolite syncline. The oreshoot varies in width from 10 to 40 ft, and in the area under consideration is about 150 ft in vertical extent, and more than 1000 ft long. Surface pits or cuts have been worked in three areas along the outcrop, with one pit just completed and a second in full production. Present production is 24,000 tons per month, of which 6000 to 7000 tons is trucked from the open pit.

Jan 11, 1954

The Climax Molybdenum Company' s newest operation is the Henderson project, which is located on the east side of the Continental Divide. Ore reserves are estimated at more than 300 million tons at a grade of 0.49% MoS2. For mining the ore a modified panel caving system is used. The ore is transported to the Henderson mill on the west side of the Continental Divide on a 42 in. (1.07 m) gauge railroad through 9.6 miles (15.4 km) of tunnel and 4. 8 miles (7.7 km) of surface track, a total distance of 14.4 miles (23. 2 km). Each train consists of 30 ore cars with capacity of 22 st (20 mt) of ore or 660 st (599 mt) per train. The unmanned trains operate completely automatically. At the 54 in. by 84 in. primary gyratory crusher, the bottom dump ore cars pass over a dump scroll to discharge at a maximum rate of 100 st (91 mt) per minute. Dumped ore falls onto a rock box before passing over a 17 ft long by 46 ft wide (5. 2 m by 14 m) grizzly set at a 40° angle with bar spacings of 7 ½ and 8 ½ in. (191 mm and 216 mm) openings. An estimated 30 to 50% of the ore (which at times is wet and sticky) passes through the grizzly. The operators report that a shallower angle on the grizzly, perhaps 35º to 37º, would have been sufficient and would have prevented impact on the back of the crusher pocket by large boulders. This pocket as well as the crushed ore pocket under the crusher is lined with AR plate. The accompanying drawings show a "future splitter" and the operators are planning the installation of this unit to prevent impact and subsequent damage to the crusher spider. Crushed ore at an 8 to 9 in. (203 mm to 229 mm) size joins the grizzly undersize in the pocket beneath the crusher. This pocket is sized at 660 live st (599 mt) so that it will accept an entire trainload of ore. Crushed ore is removed from the pocket by a four-speed, 84 in. (2. 1 m) apron feeder operating at 9.6 to 29. 3 fpm (2.9 to 8.9 mpm). A 60 in. (1.5 m) takeaway conveyor operating at 480 fpm (146 mpm) delivers the crushed ore to a 58,000 st live and 193,000 st total (52,600 and 175, 100 mt) open stockpile under an A -frame supported tripper gallery. Impact idlers on the takeaway conveyor under the apron feeder discharge are mounted on wood blocks for a cushioning effect and ripped belt detecting bars are located behind each impact idler. The conveyor tunnel is of corrugated and galvanized steel construction rather than concrete. The concrete crusher enclosure is circular in design from its lowest level at elevation minus 110 ft 4 in. (minus 33. 6 m) to elevation

Jan 1, 1978

By Garry M. Hughes

Sherritt's new, 3000 tpd, copper- zinc Fox mine is situated 30 miles southwest of Lynn Lake. The copper-zinc orebody is part of a large body of massive and semi-massive sulfides consisting chiefly of pyrite; with chalcopyrite, sphalerite (containing 7-9s Fe) and pyrrhotite in varying proportions which occur within a series of volcanic and sedimentary rocks. The average sulfide content is 67%. Higher zinc zones are masses of pyrite grains cemented by sphalerite with lower than average copper content. Zones higher in copper and lower in zinc are slightly more quartzose. Gold and silver are present in small amounts roughly proportional to the copper content. Surface diamond drilling indicated an orebody containing 12,269,000 tons grading 1.74% Cu and 2.35% Zn to the 2000 ft level. Underground drilling established the tonnage at 11,- 300,000 tons containing 1.96% Cu and 2.74% Zn.

Jan 4, 1972

By W. E. Anderson, T. M. Brady

As part of a larger study to identify factors influencing the practical operating life of wire rope used on large draglines in surface coal mining, field trips to operating surface coal mines were made during late 1975. Wire rope performance information was obtained from personnel at 13 mine sites west of the Appalachians. Seventeen pieces of equipment, utilizing bucket sizes ranging from 30 to 220 cu yd (23 to 168 m), were documented. Draglines at large US surface coal mines can be represented as 120 machines having 60-cu yd (46-m3) buckets, moving 1.8 x 10[9] cu yd (1.4 X 10[9] m3) of overburden during 6650 hours of productive availability per year. Based on the limited field study, the calculated downtime resulting from rope-related causes averages 105.6 hours per year for each typical 60-cu yd (43-m3) dragline. The total loss in production from this source alone is thereby estimated at about 25 X 10[6] cu yd (19 X 10[6] m3) annually.

Jan 11, 1979

By N. Malakouti, R. H. Whipp, O. A. Kuby, R. M. Smailer

A detailed description of the development of the FIOR process (Brown, Campbell, and Saxon, 1966) and, subsequently, other technical papers related to the operation and start up of the FIOR plant (Violetta, 1975; Whipp, 1980) are available in the technical literature. The Fluidized Iron Ore Reduction (FIOR) process plant constructed in the Matanzas region of Venezuela represents the first commercial application of this technology. The FIOR process was developed by Exxon Co. during the 1950s and 1960s. The facility in Venezuela was designed and constructed by Davy McKee, with plant start-up in 1976. While there is a minority government ownership in the company, FIOR de Venezuela operates as a private sector company with the majority of ownership being private capital. The FIOR process is well suited to utilize the naturally occurring iron ore fines of the Cerro Bolivar and San Isidro iron ore deposits located less than 100 km (62 miles) south of the plant site. Availability of natural gas within 150 km (93 miles) to the north, and a location bordering on the confluence of the Caroni and the Orinoco Rivers makes for an ideal geographic site. Feed stock to the FIOR plant consists of naturally occurring iron ore fines from these ore bodies, which are screened to -6mm (-0.2 in.) prior to drying in the ore preparation plant. A simplified flow plan is shown in [Fig. 1]. The dried ore is then transferred to the top of a structure containing four fluid-bed reactors located above one another so the mineral may flow from one reactor to the next by gravity. A reducing gas containing 90% hydrogen is made by steam reforming of natural gas, a CO shift

Jan 1, 1983

By I. H. Warren, E. Devuyst

A review of the physical and chemical aspects of the direct leaching of metal oxides has been given and com- pared to recent data of the authors and co-workers. The physical aspects, including the anisotropy of the dissolution, the hydration and the zero point of charge of some metal oxides are discussed first and then the kinetics of the dissolution of metal oxides are considered. A general mechanism of the leaching of oxides which describes most of the observed results is proposed.

Jan 1, 1973

By David Turnbull

IN isothermal recrystallization processes, new crystals generally grow into the matrix until they impinge upon other new crystals or an external surface, at constant linear rates G. Before impingement the perceptible course of growth can be described by the equation: 1 = G(t-7) C1I where, G = dl/dt, 1 is a crystal dimension measured in a constant direction, t is the time, and 7, the nucleation period, is a positive intercept on the time axis. Fig. 1 is a schematic representation of I as a function of time for a recrystallizing grain. G is dependent upon temperature, driving energy (strain or surface energy), relative grain and boundary orientations, but is generally independent of time. The frequency of nucleation, fi, (time" volume") can be defined by the equation: N = 1/fV [2] where ? is the mean nucleation period and V is the volume of the specimen that has not recrystallized. The kinetics of primary and secondary recrystallization generally can be described satisfactorily in terms of the parameters N and G only.'-" After recrystallization is complete the average grain size 7 increases with time by "normal grain growth;" didt, the average rate of grain growth, is strongly time dependent and has not yet been precisely related to G for the motion of the individual grain boundaries constituting the system. It has been suggested4* " that the elementary act in grain boundary migration is closely related to the elementary act in grain boundary self-diffusion. Although the distance of atom movement in the two processes may be somewhat different, there is reason to expect that the activated states may be very similar, so that the free energy of activation for grain boundary migration should be of the same order of magnitude as for grain boundary self-diffusion. Therefore, it is desirable to develop a satisfactory basis for comparing data on self-diffusion and grain boundary migration and to make such comparisons where possible. Theory The formal theory of grain boundary migration rates is analogous to the theory for the rate of growth of crystals into supercooled liquids reviewed elsewhere 6-8. Boreliuss has shown that the latter theory describes, within the theoretical uncertainty, the growth of selenium crystals into supercooled liquid selenium. Motto and more recently Smolu-chowski" have derived expressions for the rate of boundary migration in recrystallization. The treatment to be presented is similar to Mott's excepting that the formalism of the absolute reaction rate theory will be used. The atomic mobility, M, in grain boundary migration is defined by: G = -M6p/6x where p is the chemical potential per atom and x is the coordinate measured in the direction of grain boundary movement. Let AF be the free energy difference per gram atom on the two sides of the boundary and k the thickness of the boundary. For RT>>AF the potential gradient across the boundary (6p/6x) is essentially linear and it follows that: SF/8x = - aF/N\ [4] where N is Avogadro's number. According to the Nernst-Einstein equation, M is related to a diffusion coefficient, Do, for matter transport in grain boundary migration by the equation: M = Da/kT [5] Substituting eqs 4 and 5 into eq 3 gives the basic relation between Do and G: G = DoaF/\RT [6] Do values may be calculated from experimental values of G from eq 6 and directly compared with the coefficient of self-diffusion within the crystal, DL, or the grain boundary self-diffusion coefficient D,. However, a more convenient, though equivalent, basis for comparing atomic mobility in grain boundary migration and self-diffusion is through the constants of the absolute reaction rate theory. According to this theory diffusion coefficients may be written:" D = k2(kT/h) exp [-AF,/RT] 171 aFa, the free energy of activation, is related to the measured energy of activation, Q, by the equation: AFA = Q - T aSx - RT [8] where aSa is the entropy of activation. Substituting eqs 8 and 7 into eq 6 gives: G = ek(kT/h) (aF/RT) exp [(AS,,)C/R] exp C-Qc/RTI C91 where the subscript G refers to boundary migration. The relationship between the driving free energy and the free energy of activation in boundary migration is indicated schematically in Fig. 2. Experience indicates that the variation of G with temperature can be described by: G= Go exp [- Qc/RT] [10] where Go and Qc are generally temperature independent over wide ranges of temperature. Comparison of eq 9 with eq 10 gives:

Jan 1, 1952

By A. W. Hale

IN a work published in 1838, De Morgan, the author of the article on "Probabilities,' in the Encyclopedia Metropolitana, says " The method of least squares is not yet introduced into the affairs of common life,….that many things which are demonstrable only by the higher branches of mathematics are looked upon as useless." And he mentions an instance in which "a method was suggested for estimating the relative importance of boroughs, by considering their population and contributions to the revenue com-

Jan 1, 1881

By Robert Keeney

IMPORTANT recent developments in the melting and annealing of non-ferrous metals include: 1. Melting of nickel silver in the vertical ring induction furnace. 2. Electric melting of stereotype metal. 3. The rotary-drum gas-fired brass melting furnace. 4. The low-frequency coreless induction furnace. 5. Finishing annealing of brass sheets with city gas1 replacing wood. -in the large brass-rolling mill. 6. Electric annealing of brass and copper tubing and sheets. 7. Replacement of oil by gas and electricity in the annealing of nickel-silver shells and stampings.

Jan 1, 1930

By L. I. Hewes, Joseph W. Roe

A graphic solution of Kutter's formula for the flow of water has been worked out by Dr. L. I. Hewes in connection with his course in Graphic Computations, given in the Sheffield Scientific School, Yale University, which may be of interest to those who deal with canals, flumes and streams. 1.811 0.002811 , 41.66+ -n+-S- I Kutter's formula, V= - n 0 .00281 78- 1+(41.66 + 0.00281)7B781 is probably the most accurate of those proposed determining the flow of water. But it is extremely cumbersome, and if many calculations are to be made their solution becomes drudgery. The purpose of this chart, Fig. 1, is to furnish a rapid solution, sufficiently accurate to be well within the limits of the observed data. The chart consists essentially of three parallel scales, one for the mean velocity, V, one for the hydraulic radius, R, and one for the slope; a diagonal line, not graduated ; and a set of curves for the various values of n, the factor which involves the na-

Jan 1, 1910

By R. Simon, D. J. Graue

This paper presents correlations for predicting the solu-lility, swelling and viscosity behavior of CO2-crude oil sys8i.m~. The correlations were developed from experimental data obtained by the authors. These data are also presented. The data were determined by measuring the properties of mixtures of CO, and nine different oils. Experiinental conditions covered a range of 100 to 250°F and pressures up to 2,300 psia. Properties predicted by the correlations have average deviations, expressed as per cent of experimental value, of 2 per cent for solubility, 0.5 per cent for swelling and 12 per cent for viscosity. INTRODUCTION Interest in CO2 injection as an oil recovery process has led to the development of performance prediction methods which can be applied to specific reservoirs.1 iS To use these performance prediction methods, it is necessary to know the solubility, swelling and viscosity properties of CO2-crude oil mixtures at reservoir conditions. Some information on these properties has appeared in the literature; however, this information did not cover the range of different oils and conditions needed to prepare generalized correlations for reservoir engineering purposes. Consequently, an experimental program was undertaken to collect the data needed. The data obtained and the correlations developed from the data are described in the following sections of this paper. SOLUBILITY OF CO2 IN CRUDE OILS CO2 solubility data in the literature come from six principal sources. The solubility prediction method of Welker and Dunlop3 is limited to 80F. The information in Ref. 4 is of two types: the first includes binary and ternary mixtures of CO, and light hydrocarbons (C1 to C6), and the second gives data for CO1 and heavy hydrocarbons for a temperature range of 40 to 90F. Ref. 5 contains a KCO2 chart for systems whose convergence pressure is 4,000 psia. The KCO2's are based mainly on CO2-natural gas mixtures. Poettmann's work covered CO2 solubility in one condensate and one crude oil6,7 Ja-coby and Rzasa measured CO? solubilities as a function of pressure and temperature for two natural gas-absorber oil mixtures and two natural gas-crude oil mixtures.'8 CO, concentration in these four systems was fixed at 5 mol per cent. The work reported in this paper extends CO, solubility data to a variety of different crude oil types in a temperature range from 110 to 250F and pressures up to 2,300 psia. The experimental procedure used by the authors to obtain the solubility data consisted of combining known amounts of pure CO, and crude oil in a visual cell at a fixed temperature and measuring the bubble point of the mixture. Measurements were made for a total of 40 different CO2-oil mixtures and the results are shown in Table 2. The mixtures included nine different oils (seven crude oils and two refined oils) whose properties are listed in Table 1. All nine oils had vapor pressures less than 1 atm at the experimental temperatures. Consequently, analysis of the bubble-point vapor showed a CO, concentration over 99 mol per cent. At no time during these experiments was a second, more dense, liquid phase observed. The solubility correlation which was developed from the data in Table 2 is presented in Figs. 1, 2 and 3. In these figures, solubility is expressed as xco2 the mol fraction of CO, in the CO2-oil mixture. Fig. 1 shows solubility as a function of CO2 fugacity6 and temperature. Fig. 2 shows the same solubility data expressed as a function of saturation pressure and temperature. The solubility shown in Figs. 1 and 2 is for an oil whose UOP characterization factor is 11.7. UOP characterization factors of crude oils can be determined from Ref. 10 if the viscosity and APT gravity of the oil are known. Fig. 3 gives the solubility correction factor for oils whose UOP characterization factors differ from 11.7. The solubility correlation in Figs. 1, 2 and 3 predicted

Jan 1, 1966

By B. Thomas Mansbach

INTRODUCTION The Overseas Private Investment Corporation ("OPIC") is a U.S. Government agency mandated to promote the economic development of the less developed countries ("LDCs") by assisting U.S. private investment in the Third World. Generally, investment decisions turn on the optimism or pessimism of the private sector's financial analysis of a project, with market price of product a major unknown in a very chancy set of projections. Discussions with American mineral companies, however, show that, more often than not, in developing country projects it is the political risks of investing in mineral exploration and extraction that pose the most serious deterrent to investment. In several of the projects described here, investments would not have been made if OPIC had not been involved providing support to the project sponsors and their funding sources. Clearly it is not OPIC's business to promote U.S. investment in a project which is not commercially viable, but OPIC's programs can neutralize the political uncertainties which act as disincentives to investment in otherwise commercially viable projects. That is to say, OPIC's programs are designed to reinforce market decisions and not distort them. Although OPIC is an independent agency of the U.S. Government, it is managed by a Board of Directors, the majority of whom come from the private sector. This, coupled with the statutory requirement that it be self-sustaining and operate with due regard for the principles of prudent risk management, requires that it operate on a business-like basis. Although established as a development agency, to the business public OPIC is both an insurance company and a lending institution, with two major programs which are available to U.S. investors in the minerals sector: its political risk insurance program and its finance program. Each has been specially tailored to the meet needs of the mining industry. The insurance program provides coverage against four basic types of political risk: Currency Inconvertibility, Expropriation, loss caused by War, Revolution and Insurrection and Interference with Operations as a result of an act of War, Revolution or Insurrection. Coverage against the risks of Civil Strife can be added to both War, Revolution and Insurrection coverage and Interference with Operations. Inconvertibility coverage provides protection against a deterioration in an investor's ability to convert local currency into U.S. dollars. This deterioration can be the result of either active or passive delays. Active delays consist of a change in exchange laws or regulations that leads to inconvertibility delays of 30 days or more. For example, if the exchange regulations at the time of contract execution allow an investor to transfer earnings equal to 18% of its registered capital per annum and the government of the host country later changes the law to allow conversion of only 12%, the insured would convert the 12% transferable under the new exchange regulations with the government foreign exchange authorities, delivering the remaining 6% to OPIC for conversion at 99% of the then prevailing rate of exchange. (OPIC does not cover devaluation risks.) Upon delivery of the local currency to OPIC, normally at the U.S. Embassy in the project country, the insured's account in the U.S. would be credited with dollars. Delays can also result from what is termed passive blockage, which includes administrative delays of more than 60 days (sometimes longer) caused by the bureaucratic tie-ups or pigeonholding of transfer requests, as well as delays suffered simply because the government of the host country does not have sufficient foreign exchange. The transfer procedure is the same as with active blockage - the local currency is delivered to OPIC in the project country and OPIC provides dollars in the United States at the then prevailing rate of exchange. The second coverage -- Expropriation -protects not only against the loss of the investment due to the well-known risks of expropriation, nationalization or confiscation by the host government, but also against

Jan 1, 1985

By A. Donald Kelmers, Forest G. Seeley, B. Zane Egan

INTRODUCTION Coal ash, presently the fifth most abundant of the solid minerals produced in the United States, is expected to become the fourth most abundant by the end of this decade (1). The production of fly ash from the combustion of pulverized coal amounted to a total of 44 million metric tons (Mt) in 1977 and is expected to Increase to 91 Mt by 1985. Coal ash, which results from the Inorganic clay and mineral content of the coal, contains several elements and thus can be considered as a mined and crushed mineral resource rather than a waste material Furthermore, potential problems associated with fly-ash disposal ponds and the leaching of potentially hazardous elements through groundwater infiltration and/or rainfall provide additional incentive for processing fly ash for environ- mental control as well as for the recovery of certain metal values. Fly ash could provide an abundant domestic source of aluminum and several other metals Aluminum is now recovered from bauxite, and over 90% of this ore is imported since domestic sources are limited and cannot meet the U.S. demand There is a close relationship between the aluminum content of fly ash and the domestic consumption of this metal (Table 1).

Jan 1, 1981

By Henry Mackay

THE interesting paper recently submitted by Messrs. Tobelmann and Potter' shows that chemical problems have developed which are of great interest in this new and important branch of metallurgy. Those who realize what a process of this kind really involves will agree that it deserves a better name than "leaching process." The word leaching conveys the idea that the copper is simply leached out of the ore with acid and then precipitated on iron; the chemistry of such a process would be of little interest. As, however, during the first year's operation of this plant 24,400,532 lb. (11,067,837 kg.) or about two-thirds of the produce, was electrolytic copper, while 7,992,033 lb., or about one-third, was cement copper, it would seem more appropriate to term the process electrochemical. It further appears, from the particulars given, that efforts have been made to have the entire production in the form of electrolytic copper. -This could be done if the chemistry of the problem were kept in balance, so that it would not be necessary to discard any solutions that carried copper and acid of commercial value. A process, such as that under consideration, in which the copper is precipitated from solution by electrolysis, the solvent being at the same time regenerated, is one that requires special chemical and electrochemical knowledge and experience if all the -copper in solution that has been extracted from the ore is to be successfully and economically produced as electrolytic copper. The object of this paper is to discuss, from the practical and theoretical standpoints, the chemical and electrochemical problems involved in the working of a process of this kind, and' which must be solved to keep it in chemical and electrochemical equilibrium. In such a process, if the chemical balance is maintained, a solution can be used alternately as a

Jan 9, 1919

By Edwin F. Brush, John Chipman

Published data on the activity of carbon in binary and ternary austenite at 1000°C are reviewed. The composition variables are . The coefficient, Vj, has the value for substitutional elements but may be assigned a ualue -1 for silicon to effect a simplification on the mathematical treatment. The activity coefficient PC = is obtained from gas equilibrium data. For the ternary systems studied the Henrian activity coefficient is given by the expression: The principle advantage in cornparison with the analogous expression in terms of atom fractions is found in the fact that for most systems the final term and in many the last two terms are zero. Values of the interaction parameters are tabulated and the graphical comparison of the equation with experirt~ental data is sho,wn in several figures. The thermodynamic properties of the solid solution, austenite, are of considerable importance in the heat-treatment of alloy steels and in other aspects of ferrous metallurgy. Early studies embodied in the Fe-C diagram have been extended to include other binary and some ternary diagrams. Our best hope of obtaining a useful thermodynamic treatment of reactions in complex alloy steels will not be found in quaternary and quinternary phase diagrams but in determinations of activities and interaction relations among the several solute elements. The foundation for such a development was laid by smith' in his early studies of the activity of carbon in Fe-C alloys and his subsequent work on Fe-C-Si, Fe-C-Mn, Fe-C-Ni, and Fe-C-Co solid solutions.2"4 Other observers have also made noteworthy contributions and these will be discussed and correlated here in the light of a somewhat simplified mathematical treatment of solute interactions. Fe-C AT 1000°C In a recent review of the thermodynamic properties of binary Fe-C austenite it was shown that the simple mathematical treatment employed by smith' was capable of describing all the published results on this solution. The treatment utilizes the atom ratio, yc = nC/nF,, rather than the atom fraction. The activity of carbon is proportional to the equilibrium gas ratio, either measured on a scalk in which the activity of graphite is taken as unity or, alternatively, aC may be set equal to yc at infinite dilution. In either case the ratio aC/y = (PC, the activity coefficient. It was found that the experimental data of smith1 and those of Diin-wald and wagner; Bungardt, Preisendanz, and Lehn-ert,' and Scheil, Schmidt, and Wiinnings at temperatures of 800" to 1200° C as well as reliable data on the solubilities of graphite and cementite could be represented by the equation for which graphite is the standard state: The data on alloyed austenite have been obtained at 1000°C. For this temperature, the "Henrian" activity coefficient (which is unity at infinite dilution) is: FOr an interstitial solute such as carbon in austenite it has been shown by statistical mechanicsg that the activity in the infinitely dilute solution is proportional to the ratio of the number of lattice sites occupied by carbon to the number of yet unfilled lattice sites. A variable zz proportional to this ratio serves as a useful measure of concentration:" in which b is the number of lattice sites provided by each atom of solvent; in austenite b = 1. The Henrian activity approaches zz at infinite dilution and the ratio a is the activity coefficient. The effect of a change in concentration is then given by: It has been shown further that in some systems the derivative in Eq. [4] remains constant over a wide range of concentrations. In such a case second-order terms become negligible and the Henrian activity coefficients is:

Jan 1, 1969

By W. E. Bruce, R. J. Morrell, James Paone

This chapter is a partial summary of an investigation by the U.S. Bureau of Mines (USBM) made in response to a recent request by the Assistant Secretary, Water and Power Development of the U.S. Department of the Interior, for a comprehensive review of horizontal boring technology related to underground power-line installation. This review is concerned primarily with 3 to 36-in. diam horizontal holes from several hundred to several thousand feet in length. An electric power system consists of three essential functions: generation, transmission, and distribution. The generation component includes the generating station and step-up substation; the transmission component includes the transmission line and stepdown substation at typical voltage levels ranging from 69 to 345 kv for underground lines and 69 to 500 kv for overhead transmission lines; the distribution component includes the distribution line carrying the commonly used voltages of 120, 208, and 240 v, the distribution transformer, and the line to the service customer.l The Federal Power Commission reports that 1600 miles of underground transmission lines of 60 to 345-kv capacity are now in service in the United States. By 1980, it is estimated that approximately 3000 miles of trans- mission lines will have to be placed underground.2 The cost of burying electric transmission lines underground in metropolitan areas, approximately 30 miles from the center of each of the most populated cities, will exceed $1.5 billion with the methods now available. The wide spread in unit costs of overhead and underground transmission lines narrows as right-of-way costs for overhead transmission in congested areas increase. Improved methods of underground emplacement will certainly reduce this difference in costs and even further favor underground emplacement. Also, in the future, overhead transmission lines will probably not be permitted in highly built-up areas.

Jan 1, 1970