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By Craig R. Smith, Warren Pfefferle

Tests were conducted utilizing large flat jack devices placed in a vertical slot for high pressure loading of rock to measure in-situ properties of a rock mass. The high pressure flat jack devices were used as a site investigation tool to obtain rock mass properties. Tests were conducted before and after a 100 ton surface high explosive detonation test to assess explosive effects on the rock. It was conclusively demonstrated by these tests that meaningful flat jack tests could be successfully accomplished; also, a significantly different response of the rock medium was measured as larger areas of rock were loaded. Surface jointing was severely disturbed by the explosion.

Jan 1, 1971

By D B, M A. Sares, D W. Coulter, D C. Peters

This presentation discusses NASA-funded research on the ability of hyperspectral remote sensing to map diagnostic acid rock drainage (ARD) mineralogy that adversely affects water quality within watershed and to determine the relative contributions of natural ARD sources of metals and acidity to that drainage. Ground-based reflectance spectroscopy, combined with water chemistry, is used to identify mineralogical and chemical variations throughout a watershed. Integrated with hyperspectral data acquired from airborne remote sensing platforms, such as the NASA Airborne Visible Infrared Imaging Spectrometer (AVIRIS) sensor, a methodology has been developed that should improve environmental assessments and tracking of impacts on and from drainages. Phase I of this project focuses on a drainage basin (Lake Creek), tributary to the upper Arkansas River in central Colorado, which is impacted by natural acid rock drainage from areas of high-sulfide hydrothermal alteration. This project builds upon research and inventory efforts by the Colorado Geological Survey (CGS) to identify hydrothermal alteration that is the primary source or is contributing to acidic and toxic drainage in Colorado. This presentation will cover ground and airborne hyperspectral remote sensing techniques and results and water analyses for seasonal high-flow and low-flow conditions in Lake Creek. Identifying correlations between mineralogy, especially mineralogy that can be identified through airborne remote sensing, and water chemistry is a key focus of this project. Of particular interest are low-pH iron phases such as jarosite, ferrihydrite, schwertmannite, copiapite, and transitional amorphous phases as well as AlOH phases from higher, although still acidic, pH environments which are observed to mix with the iron precipitates within the streams draining from the hydrothermal systems. Drainage in the Lake Creek watershed derives from the Grizzly Peak caldera (Oligocene), which exhibits extensive hydrothermal alteration. Alteration types include silicic, quartz-sericite, quartz-sericite-pyrite, advanced argillic, and argillic. By understanding the chemistry of a naturally impacted drainage and its relationship to the surrounding geology, the project goal is to allow more efficient and complete identification of such sources in mineralised terranes through remote sensing technology.

Jan 1, 2003

By C Gourdon

The present study concerns a new type of mixer-settler unit where coalescence is promoted by means of the phase inversion method (MSPI). Using two different systems (alkaline etching solution û LIX 54 in kerosene and acidic aqueous solution û LIX 984 in kerosene) the influence of the total flowrate, the A/O phase ratio and the hydrodynamic conditions in the nozzles of the scattering device on the extraction and separation efficiencies are studied. Two modes of operation are clearly outlined and a theoretical model predicting the separation efficiency is proposed and compared to experimental results. A comparison between mixer-settlers with classic decanters and the MSPI unit has demonstrated the advantages of the latter where throughputs in the range 20 -25 m3.m-2h-1 can be easily realised.

Jan 1, 2000

By Helmer Hedstrom

THE purpose of this paper is to direct attention to the importance and the usefulness of phase measurements in electrical prospecting for ore, a subject about which virtually nothing has been published. The paper describes a new field method for ore prospecting, the "Turam" method, which makes use of phase measurements, and which has been used with great success for five years. Of the principal geophysical prospecting methods, the gravimetric and magnetic methods determine the direction and strength of the static fields of force of the earth. By seismic and electrical methods, fields of force are applied to the block of ground under investigation. By these methods a third parameter can be measured, besides the direction and strength of the field; namely, the time of arrival of the applied field at the different observation points. This time of arrival has been practically the only parameter measured in seismic work, while in electrical pros-pecting it has generally not been considered, the measurements having been limited to determination of direction and strength of the applied field.

Jan 1, 1937

By Dexter G. Mendoza

To analyze the behavior of minor elements in the copper smelting process, the phase relations and the activities of arsenic and antimony in the miscibility gap of Cu-Fe-S-X (X = As or Sb) system have been determined at 1473K by the quenching method and the double Knudsen cell- mass spectrometric method, respectively. The experiments have been conducted for the charges in the miscibility gap with different mass%Fe/mass%Cu ratios with varying arsenic or antimony content. The activity measurements indicate that the arsenic activities in both the metal and matte phases show extremely negative deviation from the ideal behavior. The Raoultian activity coefficients at infinite dilution in the metal and matte phases are found to be almost constant against the charges in the miscibility gap, and they are 4.3 x 10-3 and 5.5 x 10-2 for the metal and matte phases, respectively. Moreover, the activity measurements of antimony show an activity value larger than that of arsenic but it still deviates negatively from Raoult's law. The activity coefficients of antimony at infinite dilution are found to be 1.2 x and 2.2 x 10-1 for the metal and matte phases, respectively. The vapor pressures of the predominant As, AS2, AsS, Sb, Sb2, and SbS species in the gas phases of arsenic and antimony, respectively, equilibrated with the immiscible solutions have been calculated on the basis of the determined activity coefficients and they are very small at less than 1 Pa, even when their contents in the metal phase are increased up to 10 mass%.

Jan 1, 2002

By Kimio Itagaki

As a fundamental study for smelting the copper matte with high contents of arsenic and antimony in a strongly reducing condition, phase relations between the liquid matte and copper-rich alloy phases in the Cu-Fe-S-As or -Sb quaternary system and between the liquid matte and iron-rich alloy phases in the Cu-Fe-S-As or -Sb system saturated with carbon were determined at 1473 K by a quenching method. Activities of arsenic and antimony in these systems were also measured at 1473K by Knudsen cell-mass spectrometry. Furthermore, distribution ratios of silver, gold and platinum between the liquid matte and copper-rich or iron-rich alloy phases were determined in relation to the arsenic or antimony content in the systems. On the basis of these data, the elimination of arsenic and antimony from the matte to the iron-rich alloy (speiss) and the recovery of precious metals in reduction smelting of the copper matte were evaluated. It was suggested that the addition of pig iron to make a strongly reducing condition and form the iron-rich alloy, which is fluid at smelting temperatures, will be useful for fixing arsenic in the speiss.

Jan 1, 2006

By L. Voisin, K. Yamaguchi, D. G. Mendoza, K. Ltagaki

The behavior of arsenic and antimony in the Cu-0 system was thermodynamically investigated to understand their elimination during a blister-making stage in copper smelting. Firstly, the phase relations in a miscibility gap composed of the liquid slag and copper phases in the Cu-0-As and Cu-0-Sb systems at 1523 K were established by a quenching technique. It was found that arsenic and antimony distributed preferentially into the slag phase in the miscibility gap. Secondly, the activities of arsenic and antimony in the miscibility gap of these systems were determined at 1523 K by using a double Knudsen cell - mass spectrometer method. It was clarified that the activity of arsenic in the copper and slag phases showed the negative deviation from ideality while that of antimony in the copper phase a slightly positive deviation. These data obtained in this study suggest a possibility to eliminate arsenic and antimony by means of over-blowing in a converter after discharging the slag.

Jan 1, 2007

By Hector M. Henao

In order to provide the thermochemical data regarding the slag system, which are of importance for sulfide smelting and metallurgical processes but still lacking, an experimental study was carried out on the phase relations and activity of iron oxide in the FeOX-CaO-SiO2 system at temperatures between 1300 and 1400 °C and partial pressures of oxygen between 10-9 and 10-4atm. First, the solubility of CaO and SiO2 in the solid FeO were obtained and the tie lines connecting between the solid wustite (FeO) or magnetite (Fe3O4) phase and the liquid phase were determined. Secondly, iso-activity lines for FeO in the homogeneous liquid region were determined, based on the activity of iron in the Pt-crucible used in the equilibrium experiments. The activity coefficient of FeO in this region was also derived from the composition of FeO and FeO1.5 in the liquid region. Finally, the effect of (CaO/SiO2) ratio in the system and partial pressure of oxygen on these thermochemical quantities is discussed.

Jan 1, 2006

By L. Voisin, K. Itagaki

In the reductive smelting of the copper concentrate like a blast furnace operation using coke as fuel and reductant or in processing the copper concentrate which contains coal in the bulk, a sulfur-deficient matte phase often coexists with an iron base alloy in the bottom of the smelting furnace. This alloy is generally called furnace residue or speiss when considerable amount of arsenic or antimony is contained in the alloy and in the extreme case of reducing condition the alloy is saturated with carbon. As a fundamental study to know the behavior of some precious metals such as silver, gold and platinum between the sulfur-deficient matte and the furnace residue or the speiss which are in equilibrium under reducing condition, the phase relations and distribution of precious elements in the Cu-Fe-S-As and Cu-Fe-S-Sb systems saturated with carbon were determined at 1473 K by a quenching method.

Jan 1, 2007

By Florian Kongoli

The production of a homogeneous self-fluxing sinter is an important step in iron making processes. A good sinler should have good permeability and reducibility and has to keep those characteristics for a certain time. An early melt down of the sinter in the blast furnace, where its solid state reduction is essential, would cause many problems such as low permeability and reductibility. Nevertheless, the important factors that influence these characteristics, such as the chemistry of the sinter and the fluxing effect during sintering and sinter reduction conditions have not yet been clarified, In today's new reality where many new minor components such as Al2O3 and MgO enter to the sinter through raw materials, the quantification of the fluxing effects during sintering becomes even more important. In this work, the liquidus surface and phase relations of the sinter primary melts in the CaO-FeO-Fe203-Si02 system at sintering conditions have been quantified. The fluxing effect of oxygen potential, Al2O3 and MgO has also been quantified by the means of some practical diagrams that can directly help the optimization of the sintering processes.

Jan 1, 2003

By Florian Kongoli

The production of a homogeneous self-fluxing sinter is an important step in iron making processes. A good sinter should have good permeability and reducibility and has to keep those characteristics for a certain time. An early melt down of the sinter in the blast furnace, where its solid state reduction is essential, would cause many problems such as low permeability and reductibility. Nevertheless, the important factors that influence these characteristics, such as the chemistry of the sinter and the fluxing effect during sintering and sinter reduction conditions have not yet been clarified. In today's new reality where many new minor components such as Al2O3 and MgO enter to the sinter through raw materials, the quantification of the fluxing effects during sintering becomes even more important. In this work, the liquidus surface and phase relations of the sinter primary melts in the CaO-FeO-Fe203-Si02 system at sintering conditions have been quantified. The fluxing effect of oxygen potential, Al2O3 and MgO has also been quantified by the means of some practical diagrams that can directly help the optimization of the sintering processes.

Jan 1, 2003

By S. Surapunt, C. M. Nyamai, K. Itagaki

"The use of liquid copper as a medium for zinc extraction has been used in the Warner Process as a method of processing zinc-lead sulphide ore. The recovery of zinc metal is based on the reaction:ZnS(s) + 2Cu(l) = Zn(g) + Cu2S(l)In this method, thermodynamic and phase equilibria investigations of the Cu2S-FeS-ZnS and Cu2S-PbS-ZnS systems are of importance and form the basis for the liquid sulphide phase which appears as a product and is used as a solvent in the Warner Process. Phase relations in the Cu2S-FeS-ZnS and Cu2S-PbS-ZnS ternary systems were determined experimentally at 1473°K to provide a fundamental basis for the new zinc smelting process. The results show that the solid solubility of ZnS in the two systems is very small (2 wt% to 3 wt% ZnS in FeS, 4 wt% ZnS in Cu2S for the Cu2S-FeS-ZnS system; less than 0.5 wt% ZnS in both PbS and Cu2S for the Cu2S-PbS-ZnS system). The Raoultian Activity Coefficient of ZnS in the liquid mixtures and the vapour pressure of zinc over the matte in both systems is relatively large (?° = 7.7 – 15.8, Pzn(atm) = 0.088 – 1.026 for the Cu2S-FeS-ZnS system; ?° = 8.9 – 12.9, PZn(atm) = 0.075 – 0.214 for the Cu2S-PbS-ZnS system). On the FeS-ZnS join, the only phases detected are FeS and iron-rich sphalerite (Zn, Fe)S. The binary join mixture occurs at about 92 wt% FeS-8 wt% ZnS at 1473°K. Electron microprobe examination of the quenched samples indicate about 47 wt% to 48 wt% FeS in sphalerite and about 2 wt% to 3 wt% ZnS in the iron sulphide phase. On the Cu2S-ZnS join, microprobe analysis reveals that the maximum solubility is 4 wt% Zn in liquid Cu2S and 3.6 wt% Cu in solid ZnS. In the Cu2S-PbS-ZnS ternary system, microprobe analysis of the quenched samples indicate on average, 5 wt% ZnS in the liquid phase region. The only phases detected on the PbS- ZnS join are ZnS and PbS. The eutectic phase contains, on average, 13 wt% ZnS. The phase relationships, very low solid solubilities of zinc sulphide in the liquid mixtures of both Cu2S-FeS-ZnS and Cu2S-PbS-ZnS systems, coupled with the high Raoultian Activity Coefficient of ZnS as well as the high vapour pressure of zinc over matte all favour the partitioning of zinc metal into the vapour phase. This new process is cost effective and bypassesthe expensive and tedious conventionaltechnique of zinc production involving oxidationof the sulphide ore by roasting followed bya reduction process to extract the zinc. Theresults indicate that a new zinc smelting technologyusing the Warner Process would bemore efficient and preferable over the traditionalmethods of zinc extraction."

Jan 1, 2002

By Shoukun Wei, Cong Wang, Lin Cheng, Zhiyu Qiao, Jingkui Liang, Weidong Zhuang

"The subsolidus phase relations in the Sm2O3-CeO2-CuO ternary system sintered at 1000°C in air have been investigated by X-ray powder diffraction. The system can be divided into two ternary phase regions and three binary phase regions. Solid solution Sm2-xCexCuO4-y is the only ternary phase in the system. The maximum solid solubility was confirmed to be x = 0.2. The crystal structure, oxygen content and superconductivity of the solid solution Sm2-xCexCuO4-y have been investigated.I. INTRODUCTIONAfter the first discovery of the superconducting ceramic system La-Ba -Cu-O[l] with Tc = 30 to 40K, other families of cuprate-based ceramics have been synthesized with higher critical temperature. These oxides include the R-Ba-Cu-O (R: rare earth) systems (Tc=90K or so)[2,3], the Pb-Sr-(R,Ca)-Cu-O systems (T c = 50 to 100K), the Bi-Sr-Ca-Cu-O systems (Tc=80 to 105K)[4], the T1-Ba-Ca-Cu-O systems (Tc=85 to 125K)[5], the Hg-Ba-Ca-Cu-O systems (Tc=90 to 150K)[6,7], and some others. The improvement of Tc is very rapid. The measurement of the Hall and Seebeck coefficients shows that they all are p-type superconductors. In 1989, Tokura et al.[8] discovered the superconductors R2_XCexCU04_y(R = Nd, Pr, Sm) with Tc=20 to 24K (onset) and found that the charge carrier is electron in contrast to their hole doped counterparts. This discovery increases the fundamental understanding of the cuprate-based superconductors by comparing their characteristics and mechanisms to those of the p-type superconductors.One of the outstanding features of these n-type superconductors is the difficulty in obtaining samples in good charactors, such as the difficulty in obtaining zero resistivity state in single crystal or bulk samples; the semi-conductivity of bulk samples in ordinary state (opposite to the superconducting state) and a reducing reaction involved before the superconductivity has been found[9]. Therefore, it is necessary to optimize the sample preparation of the n-type superconductors. All the n-type superconductors have been found· considerable solid solubility. The compositional variations play a governing role in the carrier doping of the superconducting phases. Also, it is vital to the ceramic processing of superconductors to identify the compatible phases in the phase diagram. Finally, there is always the possibility of finding additional compounds, both superconducting and non-superconducting, in an unexplored system."

Jan 1, 1996

By Florian Kongoli

The so-called "fayalite" slag, despite problems associated with it, is the most widely used slag in copper smelting processes. Thirty years ago, in order to overcomes some drawbacks of this slag a new "calcium ferrite" slag was proposed especially for continuous copper converting. Since both slags have strong and weak points depending on the field of their application about 8 years ago another new "ferrous calcium silicate" slag was proposed that is expected to solve the drawbacks of each slag. This new slag is defined as mainly consisting of FeOx, CaO and SiO2 as its main components but it can practically have several combinations of these constituents. In order to determine the best area of this slag for possible industrial application the quantification of phase relations is an important subject. In this paper the work carried out by the authors in quantifying through an original physical model the phase relations, liquidus surface, liquidus regions, behavior of solid phases and the effect of minor components is reviewed. Several special compositions of this slag have been identified and discussed for possible applications in the industrial practice.

Jan 1, 2006

By A Vickerfält, J Huss, J Martinsson

The European Union has listed vanadium (V) as one of the critical raw materials for the transition to a future green society, as stated in the Critical Raw Material Act, written by Grohol and Veeh (2023). In the steelmaking industry based on V-containing iron ore, V is a possible by-product from the slag. A requirement for slags to be suitable for V extraction is a V content preferably above 8 wt per cent as V2O3 and a phosphorus (P) content below 0.1 wt per cent as P2O5. Hence, it is important to keep V in the slag phase while the P is moved to the metal phase during the steelmaking process.

Aug 21, 2024

By P. G. Carpenter, R. G. Nisle, F. W. Bubb

It is the purpose of this paper to describe an electrical computer which has been constructed to solve the equations for vapor-liquid equilibrium in multi-component systems. The instrument consists of seven component-computing units each with proper indicating means and power supplies. Each unit is a resistance network with a voltage matching servomechanism, and each provides an output voltage proportional to the mol-fractions for vapor and liquid phases. These voltages are summed and matched with a reference voltage to provide the solutions. Any reasonable number of such units may be put together to make a computer. The theory and operation of the computer is discussed. A number of applications and examples of computer results are given. The computer yields the over-all vapor or liquid fraction to a probable error of 0.002. An interpolation method is described which reduces the probable error to 0.0002. INTRODUCTION The process known as Flash Vaporization may be described as follows: A mixture of known composition of relatively volatile components is allowed to come to thermodynamic equilibrium at some given temperature and pressure by any path whatsoever. In general, a vapor and a liquid phase will be present at equilbrium. The problem is to determine the fractions of the mixture in the vapor and liquid phases, and to determine the mol fractions of the various components in each phase. The relations that exist between these various quantities at equilibrium are well known and will be given later. These equations are difficult to solve, yielding only to trial-and-error methods. The virtues of the analog computer are its speed and the automatic character of its calculations. The device is operated by turning a crank which varies the value of v, the total vapor fraction. This actuates a number of servomechanisms which perform automatically all computations. This computer facilitates the solution of such problems as (to mention a few] : Analysis of separator operation, studies of changes in composition of reservoir fluids with pressure decline, and analysis of natural gasoline plant operation. Examples of some of these problems are given in detail later. STATEMENT OF THE PROBLEM The essential equations are xm = 1+(km-l)v . . (1) Kmzm ym =------------------------. . (2) 1 + (Km-l)v ; n n S S xm= --------------------=1 1 + (Km-l)v m = 1 m=1 ......(3) n n S = S Km Zm =1 S ym 1 + (Km-1)v m=1 m = l ......(4) where ym = Vm/V = Mol fraction of m-th component in vapor phase. xm = Lm/L = Mol fraction of m-th component in liquid phase. Zm = Fm/F = Mol fraction of m-th component in mixture. KM = ym/xm = Equilibrium constant for m-th component at the given temperature and pressure. v = V/F = Mol fraction of vapor in the mixture. F = Total mols of a mixture of n components. V - Total mols of vapor in the mixture. L = Total mols of liquid in the mixture. Fm = Total mols of m-th component. Lm = Mols of m-th component in liquid phase. Vm = Mols of m-th component in vapor phase. Assuming the total mols of the mixture F and its composition (all the Fm) to be known — either from a quantitative analysis or from the amounts put together to make the mixture — the zm = Fm/F may be regarded as known quantities. From the given temperature and pressure of the mixture the K., are known (principally from experimental data). The primary problem is then: having given all the zm and Km to calculate v and all the fractions xm and ym. Having calculated these ratios, it is a simple matter to calculate V. L. Vm, Lm from their defining equations. SOLUTION OF THE PROBLEM Basic Computer Unit The computer consists of n units, each of which provides voltages xEo and YE, proportional to x and y as in

Jan 1, 1950

By Albert B. Horn, J. J. McKetta, O. L. Culberson

Since water is present in natural gas and petroleum reservoirs, it is of engineering value to have accurate experimental data regarding the behavior of water in hydro-carbon systems. Since experimental data of this nature are so scarce in literature, a program is under way at the University of Texas to obtain experimental data regarding the distribution of water in petroleum hydrocarbons. This initial paper is subdivided into three parts: A. The apparatus and analytical procedure are discussed. B. The equipment has been checked by comparing the experimental data with data of literature on the solubility of methane in water at 77°F and pressures to 10,000 psia. C. Experimental data are presented at 100, 160, 220, 280, and 340°F on the solubility of ethane in water at pressures to 1200 psia. As the temperature is increased the solubility of ethane in water first exhibits a minimum and then a maximum solubility. The range of applicability of Henry's Law is discussed. INTRODUCTION Although considerable experimental data have been published on water-hydrocarbon systems in the hydrate region, the information on these systems in the vapor-liquid and the vapor-liquid- 'References are given at end of paper. Manuscript received at the office of the Petroleum Branch August 31. 1949. liquid regions at elevated pressures is extremely scarce. A survey of the literature on hydrocarbon-water systems at elevated pressures was presented by McKetta and Katz12,13,14 showing the systems and phases investigated. In addition to these existing published data, Poettman and Dean" have reported the water content of propane in the three-phase region (only the propane-rich liquid and the vapor phases were studied) and Michels, et al.15 have reported the solubility of methane in water at pressures to 6800 pounds per square inch at 77°F and at pressures to 1500 psia at temperatures to 300°F. It has been shown12,14 that the presence of water will materially affect the phase equilibrium of hydrocarbon systems. In order to make experimental studies on the quantitative effect of the presence of water in naturally-occurring hydrocarbon systems, it is desirable to have data available on binary hydrocarbon-water systems. A program is underway at this laboratory to determine the phase relations of the hydrocarbon-water systems. Initially the investigation will be limited to binary systems with water as one of the components. Later ternary and complex systems will be investigated and reported. EQUIPMENT AND ANALYTICAL PROCEDURE Apparatus In order to avoid a description of the methods employed in each subsequent paper, a description of the apparatus and the analytical procedure will be given here. The apparatus is shown schematically in Fig. 1. The numbered items in Fig. 1 represent the high pressure valves. The equilibrium cell is of the totally enclosed type, with a volume of 550 cubic centimeters. The cell is mounted in an air bath which in turn is mounted on pillow blocks and connected to a rocking mechanism so that the cell and bath will oscillate approximately 30 degrees above and below the horizontal at 35 oscillations per minute. The air bath is heated by two resistance heaters. The first or primary heater is 250 watts and is controlled by a thermoregulator; the second heater is of 500-watt size and is manually controlled to aid in bringing the cell to equilibrium temperature. Air circulation in the bath is accomplished by means of a fan. the shaft of which is concentric to the heaters. The walls of the bath are insulated with 2-in. thick blocks of 85 per cent magnesia. Temperature observations are made with three calibrated thermocouples. One couple is sealed in a well provided within the equilibrium cell, and is used as the criterion of the cell being at the equilibrium temperature. The other two thermocouples are located on opposite sides of the cell to indicate temperature uniformity within the air bath. The thermoregulator, used in conjunction with a relay, gives a variation in the temperature of the air in the bath of plus or minus one degree Fahrenheit. However, since the equilibrium cell weighs approximately 55 pounds, the

Jan 1, 1950

By J. J. McKetta, O. L. Culberson

A preliminary investigation was made to determine the time required to attain equilibrium within the equilibrium cell for this system. Experimental and smoothed data are presented for the solubility of ethane in water for temperatures of 100°, 160°, 220°, 280" and 340 °F at pressures to 10.000 psia. The minimum solubility phenomenon disappears at 10,000 psia within this temperature range. INTRODUCTION .is a continuation of the investigation of the behavior of hydrocarbon-water systems, the experimental data on the solubility of ethane in water have been extended to 10,000 psia. The experimental apparatus, technique, materials, and analytical methods are essentially the same as previously reported.' TIME-CONCENTRATION STUDY Prior to the initial determinations of solubility in the ethane-water system. it was desired to establish the time

Jan 1, 1950

By Donald L. Katz, Michael J. Rzasa

With greater effort being devoted to the discovery of new oil and gas reserves and a consequent increase in bottom hole pressures due to greater drilling depths, the phase relationships of hydrocarbon fluids at pressures above 10,000 lb psi are becoming increasingly important. The present paper discusses the results of research with a windowed cell on a methane-Kensol 16 system to pressures of 25,000 Ib psi and temperatures to 260°F. Kensol 16 is a commercial high narrow-boiling-range oil. It is shown that for the temperature range of 60 °F to 260 °F, this particular system exists in two phases to pressures of approximately 14,000 lb psi, and data are presented giving the relative amounts of liquid and vapor phase? coexisting under these conditions. Partial phase diagrams are shown for six different mixtures of methane and Kensol 16, three of which include the critical region. In contrast to mixtures composed of substances of fairly close volatility. critical opalescence was noted for as much as 200°F of the critical temperature. The critical locus of the methane-Kensol 16 system was estimated and the conventional pressure-composition and temperature-composition diagrams were prepared. From these, the equilibrium vaporization factors for methane and Kensol 16 were estimated for temperatures from 60 °F to 700 °F and to pressures above 12,000 lb psi. The relations of this study to petroleum production problems and other phase equilibria research are discussed. INTRODUCTION A knowledge of the physical behavior of naturally-occurring hydrocarbon mixtures is fundamental to a thorough treatment of nearly all operations involved in the recovery, refining, and transportation of petroleum. The operations may involve the applications of phase relationships, and the relative

Jan 1, 1950

By William L. Boyd, Eugene L. McCarthy, Laurance S. Reid

Proper control of the moisture content of natural gas is essential to reliable operation of gas transmission and distribution facilities serving northern markets. The moisture content of natural gas is usually determined by dew point measurement at the existing pressure. For any gas of constant moistrire content. the dew Point varies with the pressure. A correlation of the data of several investigators is prezented in graphical form by the authors. These data were correlated by the authors and F. M. Townsend, C. C. Tsao. M. I). Rogers. Jr.. and J. A. Porter. graduate students in chemi(.a1 engineering at the University of Oklahoma. Of articular interest are the hitherto unpublished low temperature data observed by Wickliffe Skinner. Jr., which are included in this correlation. PRESENTATION OF DATA The problem of interpreting water dew points, or saturation temperatures. of natural gas in terms of specific moisture con-tent has increased in importance during the past decade bec.arl.;e of extensive development.; in the transmission and petro-chemical phases of the natural gas industry. Virtually all gas transported to northern and eastern markets must be dehydrated to a low water vapor content to prevent hydrate formation in transmission and distribution lines and resultant interruption.; in gas deliveries. Complete dehydration is required in certain phases of tile petro-chemical industry involving low-temperature operations. It is a well-known fact that the water vapor content of pure hydrocarbon vapors and their mixtures at superatmospheric pressures cannot be predicted with accuracy by assuming validity of the ideal gas laws." Earlier interest in the general problem was concentrated on the water vapor content of pure hydrocarhons and hydrocarbon mixtures in the pressure and temperature ranges common to gas and oil producing reservoirs in order to obtain fundamental data for the improvement of production techniques and the furtherance of reservoir studies. Excellent data are published for pressures ranging from atmospheric to 10,000 psig and for temperatures ranging from 100° to 460° F4,9,10,11 and are found to be in close agreement. However, experimental data at high pressures and temperatures below 100°F are comparatively limited in scope. Experimental data in the lower temperature range have been reported by Laulhere and Briscoe.8 Deaton, et al,2,3 Hammerscllmidt,5,6 and wade," In general, the pressures employed in these investigations ranged from atmospheric to 1.000 psig while temperatures ranged from 32° to 120°F; i.e., the usual conditions encountered in gas transmission line operations, Additional data were reported by Russell, et al,12 at pressures as high as 2.000 psig and covering a rather narrow atmospheric temperature range. In 1947, Hammerschmidt published a correlation of all available data,' in which the water vapor content of gases at saturation. under high pressure and low temperature. was predicted by extrapolation. In 1948, Wickliffe Skinner. Jr.. presented data on the moisture content of a low nitrogen content gas at low temperature and at pressures ranging upward to 1.500 psia.1-3 Comparison of Skinner's experimental data with the extrapolated data of Hammerscllmidt revealed an appreciable variation in the lower temperature range. emphasizing the need for a new correlation which would rely on Skinner's data at lower temperatures. Careful scrutiny of available data suggested that presence of an appreciable quantity of nitrogen in a gas mixture may affect its saturated moisture content so that data obtained from gases with more than three per cent nitrogen were not used in this correlation. CORRELATION OF DATA Data employed in this correlation are presented in Table I. The data of Dodson and Standing.4 McKetta and Katz,9 and Olds, Sage and Lacey10 were compared and found to be in close agreement so that the data of Olds. et al, re-plotted in a more convenient form by the Humble Oil and Refining Co.,' were used for temperatures of 100°F and above. Skinner's data were used for temperatures below 40°F. Between these intermediate temperature limits, the data of Hammerschmidt.7 Wade" and extrapolated data of Olds. et al.1 were tabulated

Jan 1, 1950