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By R. Hurman Eric

Within the Ag-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were re-established at 925°C by the equilibrium-quenching technique where samples were kept in evacuated and sealed silica capsules. Activities of Pb were measured by the dew-point method along the Ag-Pb binary at 925°C, 1100° and 1200°C. positive deviations were observed and the results were modeled by the Krupkowski formalism. Activities of Ag, Pb, and S, along the ternary miscibility gap were calculated at 925°C by utilizing the boundaries binary thermodynamics, phase equilibria and tie-lines. Activities of PbS within the pseudobinary Ag2S-PbS mattes were also measured by the dew-point technique and the results were again modeled by the Krupkowski formation Where negative deviations were observed.

Jan 1, 2003

By R. Hurman Eric

Within the Ag-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were re-established at 925°C by the equilibrium-quenching technique where samples were kept in evacuated and sealed silica capsules. Activities of Pb were measured by the dew-point method along the Ag-Pb binary at 925°C, 1100° and l200°C, positive deviations were observed and the results were modeled by the Krupkowski formalism. Activities of Ag, Pb, and S, along the ternary miscibility gap were calculated at 925°C by utilizing the boundaries binary thermodynamics, phase equilibria and tie-lines. Activities of PbS within the pseudobinary Ag2S-PbS mattes were also measured by the dew-point technique and the results were again modeled by the Krupkowski formation where negative deviations were observed.

Jan 1, 2003

Phase equilibria have been determined experimentally for pseudo-ternary sections of the form ?MnO?-(CaO+MgO)-(SiO2+Al2O3) with a fixed Al2O3/SiO2 weight ratio of 0.17 and MgO/CaO weight ratios of 0.25 and 0.17 respectively for temperatures in the range 1473-1673 K. The primary phase fields present for the MgO/CaO weight ratio of 0.17 include manganosite (Mn,Mg,Ca)O; dicalcium silicate a-2(Ca,Mg,Mn)O?SiO2; merwinite 3CaO·(Mg,Mn)O·2SiO2; wollastonite [(Ca,Mg,Mn)O?SiO2]; diopside [(CaO,MgO,MnO,Al2O3)?SiO2]; tridymite (SiO2); tephroite [2(Mn,Mg)O?SiO2]; rhodonite [(Mn,Mg)O?SiO2] and melilite [2CaO?(MgO,MnO,Al2O3)?2(SiO2,Al2O3)]. For the section with MgO/CaO weight ratio of 0.25 the anorthite phase (CaO·Al2O3·2SiO2) is also present. The liquidus temperatures of ferro- and silico-manganese smelting slags have been determined. The liquidus temperatures at low MnO concentrations are shown to be principally dependent on the modified basicity weight ratio (CaO+MgO)/(SiO2+Al2O3).

Jan 1, 2004

By W Y. Kim, Y B. Kang, Y J. Park

The phase equilibria in the Al2O3–TiOx system were investigated in wide ranges of temperature and oxygen partial pressure: 1300~1600°C and 10-16.6~10-8 atm, respectively. The equilibrium phases and their compositions were identified using X-ray diffraction (XRD) and electron probe microanalysis (EPMA), respectively. Most noticeably, a wide range of pseudobrookite solid solution was found in equilibrium with almost pure alumina. At each temperature, the cationic ratio expressed as RTi = nTi/(nAl + nTi)) of the pseudobrookite solid solution showed a noteworthy dependency on the oxygen partial pressure. This resulted in the formation of a broad range of pseudobrookite solid solutions, ranging from Al2TiO5 (RTi = 1/3) to Ti3O5 (RTi = 1.0). Complete miscibility within the pseudobrookite solid solution was observed at 1600°C, with only a minor miscibility gap becoming evident below 1500°C. Based on the results obtained in the present study, the behaviours of Al2TiO5 pseudobrookite have implications in two key domains: (1) understanding changes in the physical properties of the materials, and (2) elucidating the evolution of Al–Ti complex oxide inclusions in liquid steel which can deteriorate the steel cleanliness.

Aug 21, 2024

By Zhibao Li, Lanmu Zeng

The behavior of dicalcium silicate in NaOH-NaAl(OH)4-Na2CO3 solution is of significance for controlling the silica level in the production of alumina via the sintering process. Dicalcium silicate samples were obtained through a twostep approach: coprecipitation of calcium and silicate from CaCl2-Na2SiO3-NaOH solutions; and calcination of the hydrated precursor at 1200°C for 4 hours. The optimization of the synthesis parameters including temperature, solution concentrations and aging time was also investigated. Xray diffraction (XRD) and chemical analysis show that the calcined solids include dicalcium silicate with trace amounts of wollastonite. The solubility of the synthesized dicalcium silicate in HCl, NaOH, mixed NaOH-NaAl(OH)4 and NaOH-NaAl(OH)4-Na2CO3 solutions was determined. It was found that the solubility increases with increasing HCl and NaOH concentration. The effect of temperature on the solubility in HCl solutions is limited, but the solubility decreases with increasing temperature in NaOH solutions. The solubility of dicalcium silicate in NaOH-NaAl(OH)4 and NaOH-NaAl(OH)4-Na2CO3 solutions was shown to increase with increased temperature, Al(OH)3 and Na2CO3 concentration. The BromleyZemaitis model for the aqueous electrolyte system was selected to predict the solubility of dicalcium silicate. The model’s predictions yielded certain success compared with experimental solubility data.

Jan 1, 2014

By Chikabumi Yamauchi, Mitsuru Tanahashi, Tsuyoshi Taniguchi, Nobuo Furuta, Toshiharu Fujisawa

"It is essential to clarify the equilibrium relations among nonmetallic inclusions of the Mn0-SiO2-CrOx system and molten stainless steel in order to control non-metallic inclusions formed by the deoxidation of stainless steel with silicon. In the present study, the phase equilibria of the MnO-SiO2-CrOx system were measured by conducting the following experiments under controlled oxygen partial pressure, Po2, at 1873 K:1) Phase equilibria of the MnO-Cr20 3 binary system were measured for Po2 = 2 x 10-6 ~2 x 102 Pa.2) Phase equilibria of the MnO-SiO2-CrOx ternary system were measured for Po2 = 2 X 10-6 Pa.Based on the results, the phase diagram of this ternary system was established under the condition of the Si-deoxidation process of stainless steel (Po2 = 2 x 10-6 Pa and T = 1873 K).IntroductionAt the deoxidation stage in steelmaking process, generally multiple deoxidizers participate in deoxidation reactions, and the composition of deoxidation products ""non-metallic inclusions"" greatly varies depending on deoxidizing efoments and their contents. In order to control non-metallic inclusions formed by the refining process of steel, it is essential to clarify the equilibrium relations among non-metallic inclusions and molten steel.Especially, during the refining process of stainless steel, nonmetallic inclusions in molten steel seem to- change as follows. After the oxidation refining, Mn-chromite is formed in molten steel as non-metallic inclusion. By the deoxidation with silicon addition (mainly less than 1 mass%), Mn-chromite inclusions are changed their compositions to Mn-silicate. Segawa et al.[l] have reported the effect of amount of silicon addition on composition and mass ratio· of non-metallic inclusions during the Sideoxidation process of 18Cr-8Ni stainless steel at 1873 K, as shown in Figuri; L At higher silicon content than 0.5 mass%, only Mn-silicate was identified as non-metallic inclusion. On the other hand, at lower silicon content, both of Mn-chromite (MnO Cr2O 3) and Mn-silicate were identified. However, the thermodynamic and the kinetic analyses of the above-mentioned Sicdeoxidation process have not been made due to lack in the thermodynamic data for the non-metallic inclusions· of the MnO-SiO2-CrOx system, such as the phase diagrams, the activities of the components, and the free energy of intermediate compounds. In relation to the phase diagram of this system, those of the MnO-SiO2 [2] and the SiO2-Cr2O 3 [3] binary systems have been only reported"

Jan 1, 2000

By E. Haccuria

Due to the growing share of electrical cars, the use of lithium ion batteries significantly increased. Recycling of these batteries is essential to safely dispose hazardous materials as well as to recover valuables (Cu, Ni, Co, etc.). In order to optimise the recycling process, accurate information is required on the slag phase equilibria for battery smelting. The slag is a multi-component system containing alumina from the battery cases, silica and lime from fluxes, and manganese and lithium from the electrode materials. The present study accurately determined the phase equilibria in the "MnO"-Al2O3-SiO2 sub-ternary system at metal alloy saturation. Particular attention was given to the accuracy and reliability of the final results by highlighting the different reaction pathways, mass transfer- and reaction mechanisms taking place in the system during experiments. This attention enabled improved experimental methodology and measurements. Based on the present study, further measurements will be undertaken in the quaternary "MnO"-Al2O3-CaO-SiO2 system at low "MnO" concentrations, which closely represents the future recycling industrial slags.

Jan 1, 2014

By Wen-Ming Chien, Vamsi Krishna Kamisetty, Amrita Mishra, Ivan Gantan, Prathyusha Mekala, Dhanesh Chandra

"The phase equilibrium and characterization studies by using high temperature X-ray diffraction (XRD) and differential scanning calorimetric (DSC) methods have been performed for binary organic thermal energy storage materials. The organic thermal energy storage materials undergo a solid-solid state phase transition before melting which stores large amounts of thermal energy. Two materials [tris(hydroxymethyl)aminomethane(TRIS) and 2-Amino-2-methyl-l, 3- propanediol(AMPL)] were used for this study. Binary samples of AMPL-TRIS were prepared to perform high temperature XRD characterization and DSC studies and the binary AMPL-TRIS phase diagram was developed. The high temperature solid-state phases of AMPL and TRIS were characterized as a disordered BCC structure. It was found there is virtually no solubility of TRIS in AMPL or vice versa below -75 °C. The maximum solubility of TRIS in AMPL is 11% TRIS at 75 °C. The eutectoid transformation was shown at 19%TRIS-81%AMPL composition and at a temperature of 75°C. Lattice expansion calculations on single phase of TRIS and AMPL have been performed.IntroductionThermal energy storage materials can store a large amount of heat due to the presence of thermal transitions from the orientationally ordered to disordered phases occurring before melting. These molecules (such as amine and alcohol derivatives of neopentane) can reorient as a whole about the central carbon atom to form orientationally disordered crystals (ODIC) and their spherical shape makes them reorient relatively easier. Thermal energy storage materials are becoming increasingly important as a renewable energy resource. These molecules undergo large changes in enthalpies at solid-solid transitions. The presence of these compounds with large enthalpy changes are identified as potential thermal energy materials and some of die applications are solar cell systems [1-3]. Binary mixtures have been found as a way to adjust the transition properties in addition to pure compounds [4]. Tris(hydroxyrnethyl)aminomethane (TRIS, C(CH2OH)3NH2) and AMPL, CH3C(CH2OH)2NH2) are two important thermal energy storage materials."

Jan 1, 2012

By K. Itagaki, H. Henao

"The experimental study on the phase equilibrium and distribution of minor elements such as chromium and copper between magnesia saturated FeOx-MgO-SiO2 slag and Fe-Ni alloy were carried out under controlled oxygen partial pressure between 10-6-5 and 10-10 using CO and CO2 mixed gas at 1773 and 1873 K.The effect of slag additives such as lime (CaO/SiO2 molar ratio: 1) and alumina (AlO1.5/SiO2 molar ratio: 0.1) on the distribution behavior of the minor elements was also investigated.The value of distribution ratio for chromium, defined by (%Cr in slag)/[%Cr in alloy], is larger than 70 at the pO2 region conducted in the present study for the MgO saturated FeOx-MgO-SiO2 slag at 1773K. These value are almost 4-order higher then that of nickel though the distribution ratio of copper shows similar values with nickel. Analysis of the data indicates that addition of lime in the slag and the increase of temperature reduce the dissolution of chromium into the slag and the addition of aluminum increases the dissolution of chromium into the slag while reduces the dissolution of copper and nickel.IntroductionChromium. is a minor element in a nickel oxide ore but a Japan major component in the secondary material of stainless steel and is also introduced in the Fe-Ni production process due to dissolving bricks of a furnace. Chromium is a concerned matter for the beneficial utilization and disposition of ·slag because Cr6+ is a harmful element. Considering Fe-Ni as an alloy component in steel making, and the demand of high purity nickel, chromium is an -undesirable element that has to be eliminated into slag prior to the steel making, or the production of high temperature refractory alloys. On · the other ·hand chromium is an element of steel alloy for many applications, thus Fe-Ni containing chromium in minor element is desirable in some stainless steel making."

Jan 1, 2000

By X Ling, M Barati, E Moosavi-Khoonsari

In the pyrometallurgical process of secondary lead recycling, a desulfurising agent, such as Na2CO3 is added to minimise the emissions of sulfur into the atmosphere, while silica is introduced into the smelter as a fluxing material. Subsequently, a significant amount of Na2O and SiO2 remains in the downstream reverberatory furnace and blast furnace slags. However, there is limited understanding of the thermodynamic behaviour of silicate-based lead slags rich in Na2O, posing challenges in accurately determining the optimal condition for targeted metal recovery and final slag composition. In this work, the equilibrium phase relations of the PbO-Na2O-SiO2 system in the primary phase field of Na2SiO3 are studied from 800 to 1000°C via equilibration-quenching method. Samples with different compositions were prepared and held in platinum capsules in air at these temperatures to reach equilibrium. The equilibrated samples were subsequently quenched and the phase compositions were measured by electron probe microanalysis (EPMA). The results were then compared to those of previous studies and any discrepancies were resolved.

Jun 19, 2024

By Tong Gao, Jingyu Qin, Xiangfa Liu, Zengqiang Li, Yaoxian Zhang

"The recycling of aluminum materials is a green industry while Al–Si–Fe is a typical scrap aluminum alloy. The key point of recycling Al–Si–Fe alloys is to separate Al and Fe. A method by introducing Al–Si–Fe alloy into Mg melt has been investigated in this work. A separation layer with gathered Fe–rich and Al–poor Fe3Al0.7Si0.3particleswereobtained at the bottom of the cooled ingot, indicating that ß–Al5FeSi phase evolves to Fe3Al0.7Si0.3,and quantities of Al are released to the upper Mg matrix simultaneously. However, the evolution of Al3Fe by adding binary Al–Fe alloy into Mg melt is different. It is supposed that element Si plays an important role in the phase evolution procedure, thus affects the performance of this method.INTRODUCTIONThe rapid development of aeronautic, automotive and aerospace technologies strongly depends on the consumption of materials while sustainable development is the future direction. Aluminum is a recyclable material and Fe is one of the most common impurities. Fe can be introduced into Al alloys by adding low–purity alloying materials and by using unprotected ferrous crucible, tools, or equipment (Belov, Eskin, & Avxentieva, 2005; Lu& Dahle, 2005).For instance, wear–resistant rings are usually inserted into piston head when producing Al–Si pistons and an infiltration procedure by putting the cast iron rings into Al melt before casting is always essential. As a result, both the re–melting of pistons and the reuse of Al melt for infiltrating rings lead to the enrichment of Fe element, which can be even high to5 wt.%(Viala, Peronnet, Barbeau, Bosselet, & Bouix, 2002).It is widely known that coarse ß–Al5FeSi particles will form in high Fe–contained Al–Si–Fe alloys which is harmful for the mechanical properties. In the past decades, several methods to eliminate the harmful effect of ß–Al5FeSi have been investigated which can be widely referred (Munson, 1967; Lee, Kawamura, Inoue, Cho, & Masumoto, 1997; Suárez–Peña& Asensio–Lozano, 2006; Eidhed, 2008).These methods can be divided into two kinds. One is to aggregate and remove the Fe–rich phase through the methods of centrifugation, gravity filtration or magnetic separation. The other way is modifing the morphology of flake–like ß–Al5FeSi by overheating the melt or adding neutralized elements. However, these traditional methods are rarely used due to respective disadvantages, while the commonly used method in industries is using primary aluminum for dilution. However, only less than 30wt.% of scrap Al can be added into primary Al melt for each melting work while it also results in the decrease of product quality simultaneously(Zhang, Liu, & Liu, 2016)."

Jan 1, 2018

By James A. Warren

The phase field method has been successfully employed as both a tool to model heterogeneous materials and as numerical method for calculating the motion of interfaces and phase boundaries without explicitly tracking those interfaces. The method has been used to model a diverse suite of problems describing the microstructural evolution in materials. These models are derived from thermodynamic arguments and symmetry principles, and usually guarantee positive local entropy production for systems out of equilibrium. Descriptions of how phase field methods can be applied to the problems of solidification, grain growth, and electroplating will be presented.

Jan 1, 2001

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 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 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 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 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 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 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

By Laurance S. Reid, Joe A. Porter

Gas dehydration plays an important part in the production of natural gas. Effective dehydration prevents formation of gas hydrates and the accumulation of water in transmission Systems,2,6,7 insuring uninterrupted gas deliveries at maximum efficiency under the most adverse weather conditions. At the present time, most gas companies require a maximum water vapor content of seven lb per million standard cu ft of gas. so that virtually all gas tendered for sale must he dehydrated to meet this specification. For a number of years it has been common practice to produce gas and gather it at a common point for dehydration prior to discharge into the transmission system.1,3,11,16,17 However, higher transmission line pressures, long gathering lines and relatively low ground temperatures have made it necessary to dehydrate gas at. or near. individual. wells in order to gather gas from a number of newly developed fields without unusual difficulty. Where gas has been dehydrated at pressures ranging from 300 to 800 psi in the past. future trends indicate that these processes may be operated at pressures as high as 2,000 psi. Economics of gas dehydration are of great importance, partitularly where facilities must he provided to process relatively small quantities of gas, such as the production from an individual well. Although the adsorption of water vapor from gas on a granular sorbent material such as activated bauxite, activated alumina, or one of the alumina-silica gels is highly effective and produces virtually "bone dry" gas, the cost of a small unit of this type is substantially greater than that of an absorption process which, through proper selection of the absorbing liquid, will dehydrate the gas sufficiently to meet pipe line specifications. For this reason, a great deal of emphacis has been placed on the development of small, inexpensive dehydration units8,24 and the search for more effective absorb. ent liquids has been intensified. A wide variety of methods for dehydrating gas are known' and many of these have been used in industry. Earlier applications of the absorption process employed concentrated solutions of calcium and lithium chlorides as the absorbent. The severe corrosion problems inherent in handling these solutions and the relatively small dew point depressions obtained caused early abandonment in favor of, or conversion to. diethylene glycol when it was found that aqueous solutions of this organic liquid were more hygroscopic than the brines and were non-corrosive. Processes employing diethylene glycol-water solutions are widely used for gas dehydration at pressures ranging as high as 1,200 psi.13,14,15 At nominal pressures a dew point depression of 45° to 50°F may be be and the data of Russell et al." indicate that a minimum dew point is obtained from the effluent gas at a pressure of approximately 1,200 psi when the gas is in equilibrium contact with a 95 per cent by weight diethylene glycol solution. In a number of instances the dew point depression obtained with diethylene glycol-water solutions is not sufficient to produce a specification product without cooling the inlet gas. In a recent search for a better absorhent, triethylene glycol was used in a small commercial dehydration unit and subjected to rather exhaustive field tests.' The data obtained were encouraging and indicated that, at pressures ranging from 300 to 500 psi, triethylene glycol porduced a substantially greater dew point depression than diethylene glycol. These results led to an investigation of the system natural gas-water-triethylene glycol in an effort to obtain vapor-liquid equilibrium data, to determine pressure limitations, and to develop other data pertinent to the design of gas dehydration processes. A review of the literature has failed to reveal any data which permit reasonably accurate calculation of the vapor-liquid equilibrium conditions for a solution of water and triethylene glycol in contact with natural gas at high pressure. Since these constituents form a non-ideal system, the Poynting equation18,21 or the usual combination of Raoult's and Dalton's laws19,20,22 would not be valid. Correction of Raoult's and Dalton's laws by the use of activity coefficients2' is not feasible for available data are insufficient for the prediction of the actual increase in the ratio of the activity of one component in the vapor phase to its activity in the liquid. Therefore. experi-

Jan 1, 1950