Search Documents

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

By T. J. Chen

Stone coal containing vanadium is an important vanadium resource in China. Roasting and oxidation of vanadium is the foundation for extracting vanadium from stone coal. This article takes stone coal vanadium ore in Tongshan of Hubei Province as research target to conduct oxidation roasting test on it by using a self-developed low-sodium compound additive and a new optimized technology. Firstly, use potentiometric titration, X diffraction, energy spectrum and electron probe to study valence change, occurrence and phase transition of vanadium during oxidation roasting process. On this basis, primary work is done on oxidation kinetics of vanadium by exploring the steps that control reaction rate during vanadium oxidation process and determining the related dynamic parameter ? apparent activation energy. The study shows that occurrence of vanadium in stone coal of Tongshan is mainly in illite, and that the result of phase transition in roasting process is disappearance of illite containing vanadium, formation of soluble vanadate and potassium feldspar, albite. It further demonstrates that oxidation process of vanadium is step by step (V(?)? V(?)? V(?)), and its oxidation reaction is controlled by diffusion kinetics whose dynamic apparent activation energy is E1=81.19kJ.mol-1.

Jan 1, 2014

By T. J. Chen

Vanadium-beard bone coal is one of important vanadium resources in China.To extract vanadium tailings from Stone coal is produced after extracted vanadium from stone coal through the roasting, leaching and other processes. About 120-150 tons of tailings will be produced in extracting 1 ton of vanadium pentoxide. A lot of tailings that are willfully piled up have caused serious environmental pollution and wasting of resources; it is therefore necessary to realize its resource utilization. This study increases the activity of vanadium tailings by means of alkali fusion, and then uses different alkali activators to react with vanadium tailings so that geopolymer with high value added is produced. Sample of geopolymer is acquired from a mixture containing vanadium tailings, alkali activators, water and a little sodium aluminate through compression-molding process under 20MPa pressure. After cured in room temperature for three days, the maximum compressive strength of the sample can reach 36.2MPa. XRD analysis indicates quartz, the major crystal phase in vanadium tailings is decomposed,and the activity of vanadium tailings is heightened. FTIR and SEM analyses show: structural change having an important impact on the mechanical strength of geopolymer occurred during the process of vanadium tailings generating geopolymer.

Sep 1, 2012

By Wei Yin, Bin Xu, Qian Li, Yongbin Yang, Tao Jiang

Copper anode slime is an increasingly significant resource for precious metals such as Au, Ag and Pd. The extraction of Au, Ag and Pd from decopperized anode slime by different pretreatments and different lixiviants including cyanide, chloride, thiourea and thiosulfate have been investigated. When oxidizing roasting pretreatment was carried out under the conditions of roasting time 120min and temperature 625 ℃, the removal ratios of S and Sb could reach 82.18% and 98.52%, respectively. And the following alkaline leaching of calcine could result in the dissolution of 46.40% Cu and 98.48% Pb. The optima leaching ratios of Au, Ag and Pd reached 99.48%, 97.69%, 94.79% by cyanide leaching, and 95.01%, 79.84%, 96.59% by chloride leaching, and about 95.21%, 95.66%, 48.79% by thiourea/thiosulfate leaching.

Jan 1, 2015

By Wang Hao

"Demolition of reinforced concrete frame structures in building crowded cities is a hardproblem in control blasting. Any mistakes, e.g. wrong toppling direction of multi-storeybuilding or incompleted blasting of structures will all cause terrible accidents.To demolishframe structures safely, various disciplines including structural mechanics, explosionmechanics, rock engineering, etc. are involved"

Jan 1, 1993

By Li Kaihua, Li Liang, Miao Qingdong, Wang Cong

The current process of production of titanium sponge involves the use of TiCl4 as a feed material and a huge amount of heat is generated during the magnesiothermic reduction process. For this reason, it is possible to agglomerate into a titanium lump with the partial high temperature. And, it is difficult to obtain soft titanium sponge with low content of impurities. In order to solve the current problems in the titanium sponge production process, process optimization experiments study of TiCl4 feeding speed, vacuum distillation temperature, system pressure and time control had been conducted for obtain high quality titanium sponge. Experimental results show that lower feeding speed can improve the output capacity of titanium sponge and softer products can be obtained. The product grade rate of titanium sponge improved significantly.

Jan 1, 2015

By P. J. Macbeth, R. F. Overmyer, K. K. Nielson

INTRODUCTION Over the past several years, Ford, Bacon & Davis Utah Inc. (FB&DU) has been involved in research, development, and engineering activities concerning uranium mill tailings; specifically of interest in this paper are efforts in radon gas exhalation and surface flux attenuation measurements, environmental influences on radon fluxes, and basic research into radon gas behavior. Our projects have included measurements of effectiveness of specific cover material in attenuating radon surface fluxes from mill tailings, characterization of the parameters in cover materials and tailings that influence radon exhalation, long-term tailings stabilization planning, determination of the effects of moisture on radon emanation and diffusion from ores, and determinations of baseline radon fluxes. Our efforts have been sponsored by U.S. Department of Energy, the U.S. Nuclear Regulatory Commission, Tennessee Valley Authority, the commercial uranium industry, and we are presently engaged in efforts for the U.S. Bureau of Mines. Much of the material presented in this paper is taken from our published reports on radon flux attenuation and tailings stabilization (Macbeth et al., 1978; Nielson et al., 1980; Rogers et_ al., 1980; Thamer et al al., 1980). CHARACTERIZATION OF RADON GAS EXHALATION One dimensional diffusion theory based on Fick's laws is the basis for the modeling of radon gas migration through large quantities of porous tailings and cover materials applied over the large areas of tailings piles. Fick's first law relates the gaseous concentration gradients to the flux over the entire surface and defines the effective diffusion coefficient De as: [ ]

Jan 1, 1980

By R. E. Moore

The lining systems currently in use in BOF furnaces, certain steel ladles, and the slag line of electric are furnaces were developed during the late seventies through the mid-eighties using a trial and error method of combining aggregate, carbon sources, additives and binders. They are currently based on magnesia, graphite, metal additives and resin binders, the selections of each being tied to the anticipated intensity of the use conditions. The general functions of the respective constituents are well appreciated, however, there is still a great deal that is not known about how the socalled antioxidants protect the graphite nor how impurities from the graphite and the aggregate enter into the wear processes. In a simplified assessment of wear processes, it appears that if the deoxidized layer can be kept very thin, less than 810 mm in depth, and if the viscosity and quantity of the matrix glassy phases can be controlled to resist erosion of the deoxidized layer, lining life can be maximized for the various applications. This paper will discuss the characteristics of the starting materials systems currently being employed for applications requiring a deoxidation function to realize extended wear. It will not attempt to explain all the complex interrelationships between the respective constituents but will point to the potential for improvements through the use of improved constituents.

Jan 1, 1991

By Runsheng Xu, Haiyang Wang, Pengcheng Zhang, Tengfei Song

Semi coke, a byproduct in the chemical industry, is a new fuel for blast furnace injection in China. In this study, semi coke and bitumite were milled into different size, ranged from 0.147mm to under 0.074mm. The content of volatile matter and ash, which affect the combustibility of semi coke, were measured using muffle furnace. The mixture, in which the proportion of coal in different sizes changed, was blend by semi coke and bitumite with different size. Activation energy calculation and the comprehensive combustion characteristic index of all kinds of blends was also discussed. The result obtained by Thermogravimetry –Derivative Thermogravimetry curves indicates that the smaller the size of mixture is, the lower for the characteristic temperature, and the better for its combustibility, Semi coke can be a substitute for anthracite in blast furnace injection.

Jan 1, 2015