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THE Institute of Metals Division of the American Institute of Mining and Metallurgical Engineers appointed a Research Committee in 1925 to de-termine what could be done by the Division to promote research work in the United States on non-ferrous metals. It was recognized that a considerable volume of use-ful research work in this field was being carried on by individual industrial companies as well as by the uni-versities and other research institutions, such as the Bureau of Standards. One need only refer to the recent research literature on non-ferrous metals in the TRANS-ACTIONS of the A.I.M.E., and elsewhere, to be con-vinced of healthful research activity in this field. The appointment of the Committee, however, voiced the impression that what was being done was, however excellent, inadequate for the needs of the industry. It was felt that the Division could usefully devote some of its time and effort in stimulating activity in this field. The deliberations of the Research Committee have not failed to develop wide differences of opinion even on the simple questions: (1) whether the Division can aid in any practical manner in this cause and (2) what the features of such aid might be. However, it was clear that there was only one type of research activity with which it could be very usefully concerned, viz., that on subjects of fundamental interest and general application. It was obvious that research work having special objects and more immediate commercial appli-cation should best be left to the industry itself.

Jan 1, 1927

By Xiao-hui Fan, Xu-ling Chen, Zhi-yuan Yu1, Guanghui Li, Min Gan, Yun-song Huang, Tao Jiang

Compared with the traditional de-NOx processes by cleaning the waste gas, a new approach for reducing the formation of NOx during sintering process is proposed. Since more than 90vol% of NOx comes from the fuel combustion, the influence of sintering coke breeze pretreated by CO(NH2)2 additive on the NOx emission is researched. As adding CO(NH2)2, the reduction agents (NHi) are generated during the pyrolysis of CO(NH2)2, which reinforce the NOx reduction, And the appropriate content of CO(NH2)2 is 1.0 mass% of coke breeze.

Jan 1, 2015

By Duanyou Li, Qing Xiao, Zhiwang Wang, Xiaoqing Gan

"Seepage is a major cause of earth-rockfill dam failure. Numerical simulation of infiltration process, distribution of drift, flow velocity and direction after the impoundment can guide seepage control and evaluate its effects. A double field coupling model is established based on soil consolidation theory and the interaction between the seepage field and the temperature field. The simulation is implemented under the situation of core wall setted, core wall not setted, and core wall setted with concentrated leakage. The results indicated that the saturation line height was significantly reduced due to impervious core wall, and the temperature distribution is uniform above the saturation line. If concentrated leakage occurs, temperature distribution of dam was significantly changed, which is consistent with theoretical inference.INTRODUCTIONEngineering seepage field distribution must be calculated in seepage control design, optimization, and correction of new engineering construction of earth dams, as well as in seepage monitoring and evaluation of existing earth-rockfill dams. The aim of calculation is to identify the important parameters in seepage field, such as the coefficient of permeability, seepage flow, pressure, head, and allowable seepage slope, for effectively implementing seepage control design, correction, safety assessment, and anti-seepage reinforcement. These seepage parameters usually can be obtained by in-situ test and back-analysis based on reliable monitoring data.In order to obtain reliable monitoring data and reflect the earth-rockfill dam seepage state and change process, appropriate monitoring technology and monitoring method is necessary. The traditional seepage monitoring method is through site inspection and sensors (e.g., osmometer, piezometric tube and measuring weir) that buried in the structure and its foundation. However, there are still some disadvantages:"

Jan 1, 2015

By C. R. Tang

Due to the current lack of sufficient occupational hazards supervisory staff in China, an occupational hazards supervision regulatory framework is proposed, based on the cloud. Data on respirable dust, noise, heat, toxic and hazardous substances and protection facilities are uploaded to private cloud computing data and service centers to build an occupational hazards supervision system. This system promotes occupational hazards governance. Complex reports are generated. Through the establishment of an occupational hazard supervision data threshold, the dynamic regulation of occupational hazards is accomplished. The main characteristics of this approach are low cost, ease of expansion and maintenance, and strong performance.

Aug 1, 2013

By X. H. Li, F. Xie, Q. Zhang, Z. H. Shen, S. Mao

"There is abundant rare-earth element(REE) in our country, but it is very fragmented in the earth's crust, and it is very difficult to mining or mining cost is extremely high. There are few of industrial value rare-earth deposits. There is a lot of concomitant rare-earth deposits, and the comprehensive utilization value is high. There is very rich carlin-type gold resource, associated with a certain amount of REE in the southwest of Guizhou province. In order toutilize comprehensively the resources, this paper conducts the study on the occurrence characteristics of REE in the ore. By the chemical analysis, the gold grade is 3.35g/t, the organic carbon 0.81%, the total REE 0.022%, which is a high carbon fine disseminated gold ore. By the optical microscope and XRD analysis, the major minerals are quartz, pyrite, calcite, limonite, arsenopyrite, mica, kaolinite, clay minerals, etc. In addition, there is a large amount of carbonaceous materials, such as organic carbon, graphite, which is harmful on leaching of gold. By the scanning electron microscopy analysis, there are thorium, lanthanum and neodymium, ytterbium, persimmon and other REE in the ore. Gravity separation shows that REE could be enriched to lighter material mainly, which indicates that REE disseminate closely with lighter materials.INTRODUCTION Carlin-type gold ore is important gold resource in the world, which are mainly distributed in Nevada and its vicinity, as well as the two Golden Triangle of Yunnan, Guizhou, Guangxi and Sichuan, Shanxi, Gansu province in China(Su W.C. et al.,2009; Xia G.X.,1996).Guizhou carlin-type gold ore is the second largest gold resource in the world(Muntean J L et al.,2011), distributing along the southwestern margin of the Yangtze plate, mainly mineralizing in the neopaleozoic-early mesozoic(Xie Z J et al.,2017). Many large gold deposits have been found in southwest in Guizhou in twentieth century, such as Zimuyou,Getang, Lannigou, Shuiyindong and Laowanchang gold deposit, and so on, and the gold reserves reach over 100 tons(Xia Y. et al.,2009).There is a certain amount of rare-earth resource in the carlin-type gold ore in the southwest in Guizhou province, and the current researches might mainly focus on characteristics of REE from the angle of geological mineralization(AnanyevY.,2015), not from the angle of separation and enrichment."

Jan 1, 2018

By Masaharu Moteki

At present, the Unmanned Construction System (UCS) is adapted on initial operation against the disaster. For instance, it has been used in Unzen. When the scale of the disaster is big, or the danger to a person is big, the UCS is expected as a quick and safe construction technology. The Remote Controlled UCS is introduced into construction site to repair earth-fill embankment or to remove rock, as urgent measures after the disaster outbreak. For improvement of the operability, shortening of the skill time, reduction of the fatigue, examination of the most suitable system (placement of a monitor and the joy stick) of the remote system is a main theme in the Public Works Research Institute (PWRI). In the report of this year, when the operator controls construction machine directly or he controls it using remote system (he can check the situation of site only via monitor), the degree of achievement, construction efficiency and construction precision were inspected. The remote system which is based on the system used at Unzen was developed at PWRI.

Aug 1, 2013

By Zhiqiang Zhou, Libin Zhu, Zizong Zhu, Hao Xiong, Yuchuan Ding

In order to utilize the lean ore resources from XinJiang rationally and optimize mixture, laborarory measurements have been carried out under different basicity, various mixed carbon content as well as the properties (ratio) of fuel particle size by the sintering pot for further microstructure analyses. The results show that sinter strength falls by 5.0%, low temperature reduction disintegration index (RDI) drops off to the lowest in certain ranges. The natural degradation index of sinter is much higher when sinter basicity is between 1.65 and 1.75. The sinter strength increases when sinter basicity is between 1.75 and 2.0. Meanwhile, the sinter strength and RDI +3.15 improve with increasing carbon content. And the sinter strength and RDI+3.15 both decrease with the decrease of the distribution ratio of small fuel particle, thereby decreases the yield of sinter. Microstructural analyses have been investigated to figure out the mechanism of the influence of the three factors on sinter.

Mar 1, 2017

By Guangliang Wu, Dongchang Huang, Xinbin Liu

Oxidation Kinetics of SPHC was analyzed by TGA, and the curve of oxidation weight gain with different temperature was acquired. It is found that, when the oxidation temperature is between 500 and 600 , all the curves are linear; when the oxidation temperature is above 700 , the curves are close to parabolic. At the temperature of 900 , the oxidation weight gain increases dramatically. The TGA results indicate that the activation energy of SPHC steel is 146.19 kJ/mol at the temperature of 500 900 , and an oxidation kinetic model was set up for variable temperature. Based on the temperature change during rolling process, numerical simulation of oxide scales evolution was carried out for SPHC steel, and the simulation result agreed well with measured ones. It can provide a basis for estimating the scale growth and controlling the temperature on site.

Jan 1, 2016

By B. H. Sage, W. N. Lacey

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By W. N. Lacey, B. H. Sage

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By Riki Kobayashi, D. L. Katz

The conditions at which methane and water form solid hydrates have been extended from 4,000 to 11,200 pounds per sq. in. The curve at high pressure had been in doubt because of Villard's report of a critical decomposition temperature. The paper explains the nature of the hydrate curve at high pressure and its dependence on fluid phase behavior. Extropolation of the methane hydrate curve indicates a pressure of 40,000 pounds per sq. in. will cause hydrates to form at a temperature of 100" F. INTRODUCTION The conditions under which natural gases form hydrates when liquid water is present have been studied by several investigators up to pressures of about 4,000 pounds per sq. in. The early work by Villard on hydrates of methane and ethylene13, ethane'', and propane14 included references to critical decomposition temperatures of the hydrates. Villard's work raised the question as to whether the pressure-temperature curve for methane-water hydrate continued above a temperature of 70.7°F. or whether this was the maximum temperature at which hydrates would form. This paper extends the experimental data on methane hydrate to 11,200 pounds per sq. in. A discussion of phase relations in the hydrate region for the hydrocarbons and of the methane-water system at high pressures is included. PREVIOUS WORK Villard suspected that methane hydrates could not be formed at temperatures above 21.5°C. (70.7°F.)la irrespective of the pressure of the liquid-vapor system. However, he was limited in his studies by his apparatus in 1888 to pressures not greater than 300 atmospheres (4,410 pounds per sq. in.) so that there has remained some doubt as to the existence of such a maximum temperature in this region. For the case of ethylene hydrates, however, Villard does specifically state the occurrence of what he terms a "critical temperature for the decomposition of the hydrates"13. Fig. lB shows a pressure-temperature projection of the three-phase locus, hydrate-ethylene rich liquid-vapor (H-L2-V) terminating at the critical locus in which L² and V assume similar properties. Throughout this paper the following phase designations will be used: H for hydrate, Ll for the water rich liquid. L2 for the

Jan 1, 1949

By Riki Kobayashi, D. L. Katz

The conditions at which methane and water form solid hydrates have been extended from 4,000 to 11,200 pounds per sq. in. The curve at high pressure had been in doubt because of Villard's report of a critical decomposition temperature. The paper explains the nature of the hydrate curve at high pressure and its dependence on fluid phase behavior. Extropolation of the methane hydrate curve indicates a pressure of 40,000 pounds per sq. in. will cause hydrates to form at a temperature of 100" F. INTRODUCTION The conditions under which natural gases form hydrates when liquid water is present have been studied by several investigators up to pressures of about 4,000 pounds per sq. in. The early work by Villard on hydrates of methane and ethylene13, ethane'', and propane14 included references to critical decomposition temperatures of the hydrates. Villard's work raised the question as to whether the pressure-temperature curve for methane-water hydrate continued above a temperature of 70.7°F. or whether this was the maximum temperature at which hydrates would form. This paper extends the experimental data on methane hydrate to 11,200 pounds per sq. in. A discussion of phase relations in the hydrate region for the hydrocarbons and of the methane-water system at high pressures is included. PREVIOUS WORK Villard suspected that methane hydrates could not be formed at temperatures above 21.5°C. (70.7°F.)la irrespective of the pressure of the liquid-vapor system. However, he was limited in his studies by his apparatus in 1888 to pressures not greater than 300 atmospheres (4,410 pounds per sq. in.) so that there has remained some doubt as to the existence of such a maximum temperature in this region. For the case of ethylene hydrates, however, Villard does specifically state the occurrence of what he terms a "critical temperature for the decomposition of the hydrates"13. Fig. lB shows a pressure-temperature projection of the three-phase locus, hydrate-ethylene rich liquid-vapor (H-L2-V) terminating at the critical locus in which L² and V assume similar properties. Throughout this paper the following phase designations will be used: H for hydrate, Ll for the water rich liquid. L2 for the

Jan 1, 1949

By J. S. Billheimer, H. H. Reamer, B. H. Sage

Jan 1, 1949

By H. H. Reamer, B. H. Sage, J. S. Billheimer

Jan 1, 1949

By J. S. Billheimer, B. H. Sage, W. N. Lacey, C. G. Yundt

As a part of a general investigation of the separation of bitumen from hydrocarbon mixtures a study was made of a restricted quaternary system composed of methane, decane, tetralin, and bitumen. The work was limited to a pressure of 8000 psi, a temperature of 220 °F, and to a fixed relative proportion of decane, tetralin, and bitumen. The measurements permitted the determination of the distribution of these components in each of the fluid phases. It was not possible to distinguish a second liquid phase in the course of these measurements. Gas-liquid equilibrium "constants" of each of the components were found to vary markedly with the composition of the system while temperature and pressure remained fixed. INTRODUCTION The separation of bitumen frorn naturally occurring hydrocarbon mixtures has been of importance for a number of years in the production of petroleum, especially in the California area. The deposition of this material from crude oils was noted in earlier studies of the solubility of natural gas in crude oil.¹,²,3 Studies of the separation of bitumen from crude oils from the Greeley and Santa Fe Springs fields were carried out."." The behavior of these systems appeared complex and studies of two restricted ternary systems involving mixtures of n-pentane, tetralin, and bitumen,' and of decane, tetralin; and hitumen, confirmed this belief. Reviews of the literature pertaining to the separation of bitumen from naturally occuring and refined hydrocarbons are available." The important effect of methane in the separation of bitu- men from naturally occurring hydrocarbon mixtures was apparent from the earlier studies and for that reason it appeared desirable to investigate a restricted quarternary system involving mixtures of methane. decane, tetralin, and bitumen; data concerning the behavior of mixtures of decane. tetralin. and bitumen having already been obtained.V his study was restricted to a pressure of 8000 psi," a temperatue of 220° F, and fixed relative proportions of bitumen, decane. and tetralin. This composite constituent, hereinafter designated as the less volatile constituent, was made up of 0.0455 weight fraction bitumen. 0.0909 weight fraction decane, and 0.8636 weight fraction tetralin. The experimental method involved bringing together mixtures of methane and the less volatile constituent in varying proportions in a constant volume container at the pressure and temperature indicated above. The composition of each of the phases was determined and from this the extent of the separation of bitumen was established. MATERIALS The bitumen used in this investigation was obtained from the same stocks employed in earlier studies. The crude material from the North Coles Levee field was stored in the laboratory] in a closed drum for a period of five years. Several samples from this stock were subjected to refining operations which were described earlier,' and every effort was made to follow the same procedure in all cases. It was necessary to prepare supplies of bitumen for this investigation at two rather widely different times. These materials have been identified as samples 1 and 2. The composition of the crude bitumen after it was washed with n-pentane at room temperature

Jan 1, 1949

By W. N. Lacey, C. G. Yundt, B. H. Sage, J. S. Billheimer

As a part of a general investigation of the separation of bitumen from hydrocarbon mixtures a study was made of a restricted quaternary system composed of methane, decane, tetralin, and bitumen. The work was limited to a pressure of 8000 psi, a temperature of 220 °F, and to a fixed relative proportion of decane, tetralin, and bitumen. The measurements permitted the determination of the distribution of these components in each of the fluid phases. It was not possible to distinguish a second liquid phase in the course of these measurements. Gas-liquid equilibrium "constants" of each of the components were found to vary markedly with the composition of the system while temperature and pressure remained fixed. INTRODUCTION The separation of bitumen frorn naturally occurring hydrocarbon mixtures has been of importance for a number of years in the production of petroleum, especially in the California area. The deposition of this material from crude oils was noted in earlier studies of the solubility of natural gas in crude oil.¹,²,3 Studies of the separation of bitumen from crude oils from the Greeley and Santa Fe Springs fields were carried out."." The behavior of these systems appeared complex and studies of two restricted ternary systems involving mixtures of n-pentane, tetralin, and bitumen,' and of decane, tetralin; and hitumen, confirmed this belief. Reviews of the literature pertaining to the separation of bitumen from naturally occuring and refined hydrocarbons are available." The important effect of methane in the separation of bitu- men from naturally occurring hydrocarbon mixtures was apparent from the earlier studies and for that reason it appeared desirable to investigate a restricted quarternary system involving mixtures of methane. decane, tetralin, and bitumen; data concerning the behavior of mixtures of decane. tetralin. and bitumen having already been obtained.V his study was restricted to a pressure of 8000 psi," a temperatue of 220° F, and fixed relative proportions of bitumen, decane. and tetralin. This composite constituent, hereinafter designated as the less volatile constituent, was made up of 0.0455 weight fraction bitumen. 0.0909 weight fraction decane, and 0.8636 weight fraction tetralin. The experimental method involved bringing together mixtures of methane and the less volatile constituent in varying proportions in a constant volume container at the pressure and temperature indicated above. The composition of each of the phases was determined and from this the extent of the separation of bitumen was established. MATERIALS The bitumen used in this investigation was obtained from the same stocks employed in earlier studies. The crude material from the North Coles Levee field was stored in the laboratory] in a closed drum for a period of five years. Several samples from this stock were subjected to refining operations which were described earlier,' and every effort was made to follow the same procedure in all cases. It was necessary to prepare supplies of bitumen for this investigation at two rather widely different times. These materials have been identified as samples 1 and 2. The composition of the crude bitumen after it was washed with n-pentane at room temperature

Jan 1, 1949

By J. S. Billheimer, B. H. Sage, W. N. Lacey

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.' Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2'3'4'5'6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made' and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."' The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949

By W. N. Lacey, B. H. Sage, J. S. Billheimer

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.' Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2'3'4'5'6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made' and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."' The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949