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By P. Dhar, H. R. Kota, M. Thornhill

A very high-grade calcite deposit located in northern Norway consists of CaCO3 ore with minor silicate and sulphide impurities. Cationic (Tallow-1,3-diaminopropane, Duomeen T) collector has been used in the purification of calcite by flotation with an aim of achieving calcite concentrate for its use in value-added products in a variety of industries. The feasibility of sulphide flotation from calcite by this cationic collector has been initially judged from Hallimond flotation and zeta potential on pure mineral systems and the results illustrate the removal of sulphide from calcite ore at neutral pH region. The adsorption mechanism of diamine on both the sulphide minerals was found to be the same by zeta potential studies. The variations in zeta potential are in good agreement with the adsorption of diamine molecular and ionic species as a function of pH. FTIR studies also showed the adsorption of diamine species in agreement with the zeta potential and Hallimond flotation results. Furthermore, the removal of sulphide impurities with selective flotation by diamine collector was performed in bench-scale flotation with the calcite ore and the results indeed showed that the calcite concentrate could meet the quality requirements for its use in the paper industry for coating and filler purposes.

By Gen Kamimura, Hiroyuki Matsuura

Zinc is widely used for galvanization of steel plates due to its high corrosion resistance. Steel scraps containing waste zinc-coated steel plates are remelted for recycling of steel in electric arc furnace (EAF) process, in which zinc is concentrated in EAF dust ranging from 10 to 40 mass%. Therefore, recycling of zinc from EAF dust is important to secure zinc resource. Our group has proposed selective chlorination and evaporation method recovering zinc as a form of chloride from EAF dust. Since recovered zinc chloride may contain lead, iron and copper as impurities, purification of zinc chloride is essential for production of highly pure metallic zinc. In the present study, removal of lead chloride from molten zinc chloride-alkali chloride by cementation reaction adding zinc was investigated. Experimental results were analyzed and discussed thermodynamically and kinetically as well as the feasibility and limitation of this process were examined.

Mar 1, 2018

By K. C. Nathsarma

An attempt was made to extract niobium oxide from ~98.5% Nb2O5 using solvent extraction processes. Nb2O5 is used as the feed material in carbothermic reduction processes aimed at producing high-homogeneity, super-conductor-grade niobium on a laboratory scale. The Nb metal used for superconductor applications requires a residual resistivity ratio (RRR) > 300, which in turn needs a stringent purity of Nb and allows impurities (substitutional and interstitial) in ppm levels only. In this paper, solvent extraction of niobium was studied under various experimental conditions, such as effect of different extractants, concentration of methyl isobutyl ketone (MIBK) in the organic phase and concentration of various acids. The concentrate was digested with hydrofluoric acid, with ammonium fluoride (NH4F) as a stripping agent. The extraction of niobium from low hydrofluoric- (HF-) bearing solution was found to be low. Thus, various concentrations of hydrofluoric acid and sulfuric acid, as well as hydrofluoric acid and hydrochloric acid, were investigated towards obtaining a maximum amount of niobium in the filtrate and a minimum amount of niobium in the residue. A McCabe - Thiele plot for extraction of niobium from the aqueous phase, HF-bearing solution using HCl with 85% MIBK in kerosene has been constructed to determine the O:A ratio and the number of stages of the process.

Jan 1, 2011

By K. C. Nathsarma

An attempt was made to extract niobium oxide from ~98.5% Nb2O5 using solvent extraction processes. Nb2O5 is used as the feed material in carbothermic reduction processes aimed at producing high-homogeneity, superconductor-grade niobium on a laboratory scale. The Nb metal used for superconductor applications requires a residual resistivity ratio (RRR) > 300, which in turn needs a stringent purity of Nb and allows impurities (substitutional and interstitial) in ppm levels only. In this paper, solvent extraction of niobium was studied under various experimental conditions, such as effect of different extractants, concentration of methyl isobutyl ketone (MIBK) in the organic phase and concentration of various acids. The concentrate was digested with hydrofluoric acid, with ammonium fluoride (NH4F) as a stripping agent. The extraction of niobium from low hydrofluoric- (HF-) bearing solution was found to be low. Thus, various concentrations of hydrofluoric acid and sulfuric acid, as well as hydrofluoric acid and hydrochloric acid, were investigated towards obtaining a maximum amount of niobium in the filtrate and a minimum amount of niobium in the residue. A McCabe - Thiele plot for extraction of niobium from the aqueous phase, HF-bearing solution using HCl with 85% MIBK in kerosene has been constructed to determine the O:A ratio and the number of stages of the process.

Nov 1, 2011

By Georgios N. Anastassakis, Nickolaos Georgiou

"Soil contamination by oil as well as by other organic pollutants poses a major problem to the environment. Various methods have been used to remove organic contaminants from soil, such as: biological, thermal, chemical and physical. Methods based on Mineral Processing principles have also been used (cyclone separation, gravimetric separation, attritioning and washing). This paper studies the possibility to remove a rich-in-contaminant soil fraction by applying flotation. The contaminated soil was artificially prepared by mixing soil with diesel fuel. Sodium dodecylsulfate (SDS) and a tertiary amine (TA) were used as collectors. The effect of collector quantity added and conditioning time was studied. The results showed that the removal of a rich-in-contaminant soil is feasible while a clean fraction is also obtained. In several cases, the removal of oil-contaminated soil approaches or reaches 100%. Introduction Human activities are intimately associated with environmental pollution to the air, water and soil, as well. Soil pollution from inorganic and organic compounds is of equal importance with that of air and water, as it results in soil degradation and its concomitant problems with respect to meeting the human needs (house building, agriculture etc). Heavy metals along with their compounds are encountered among the most usual soil inorganic pollutants. The corresponding organic soil-pollutants are oil, oil-derivatives, pesticides, various aromatic (benzene, phenols, cresols, toluene etc) and poly-aromatic (naphthalene, anthracene etc) hydrocarbons, as well as various other organic compounds (pyridine, cyclo-hexane etc). Oil remains the basic energy source sharing 38% of the global needs, being followed by coal and gas with a share of 26 and 21% correspondingly [1]. The entire activities related with oil production, transport and consumption promote pollution in the air, water and soil. Consequently, soil pollution from oil is favoured at refineries, storage sites (due to possible pipe and tank leakage, tank cleaning works, loading and transportation) and, finally, at the oil-selling sites. Oil (or diesel-oil) fuel is a mixture of hydrocarbons, with 10-20 carbon atoms in the chain of each. It is mainly composed of paraffins, naphthenes and various aromatic compounds. In general, oil is composed of 20-30% in aromatic compounds, 5-6% in naphthenes and the rest is paraffins [1]."

Jan 1, 2008

By Edward Wichers

THE purpose of this paper is to set forth the matters of principal interest in connection with work done in the past few years on the purification of the metals of the platinum group, including the study and modification of methods already in the literature and the development of new procedures. For the most part, the results will be given in summary form, reserving the publication of detailed data and directions for a forthcoming paper to be issued by the Bureau of Standards. In recent years increasing interest has been shown in the preparation of the pure platinum metals, both by those concerned with the manufacture of the metals and their alloys for scientific and industrial purposes and those who are engaged in the study of the chemical or physical properties of the elements. The purification of the metals usually has been regarded as a matter so involved and difficult as to require the attention of specialists. It is hoped that this paper will show that any of the metals can be prepared in any desired degree of purity by relatively simple straightforward chemical methods. For the most part, it is thought that the methods given are suitable for small-scale refineries as well as for the laboratory; also, that they will bring the time required for the purification of any of the metals within reasonable limits. The new procedure suggested for purifying platinum should prove to be much shorter than any methods described in the literature.

Jan 1, 1928

By Edward Wichers

THE purpose of this paper is to set forth the matters of principal interest in connection with work done in the past few years on the purification of the metals of the platinum group, including the study and modification of methods already in the literature and the development of new procedures. For the most part, the results will be given in summary form, reserving the publication of detailed data and directions for a forthcoming paper to be issued by the Bureau of Standards. In recent years increasing interest has been shown in the preparation of the pure platinum metals, both by those concerned with the manufacture of the metals and their alloys for scientific and industrial purposes and those who are engaged in the study of the chemical or physical properties of the elements. The purification of the metals usually has been regarded as a matter so involved and difficult as to require the attention of specialists. It is hoped that this paper will show that any of the metals can be prepared in any desired degree of purity by relatively simple straightforward chemical methods. For the most part, it is thought that the methods given are suitable for small-scale refineries as well as for the laboratory; also, that they will bring the time required for the purification of any of the metals within reasonable limits. The new procedure suggested for purifying platinum should prove to be much shorter than any methods described in the literature.

Jan 1, 1928

By S. Fazluddin, K. C. Sole, M. R. Serwale, T. Coetsee

The CSIR-Ti process employs lithiothermic reduction of titanium tetrachloride feedstock to produce titanium sponge. The product is therefore contaminated by a range of lithium and chloride species. In this study we examine the effects of particle size, temperature, and HCl concentration as input leaching variables on the removal of chlorides from the crude titanium sponge. A review of the aqueous chloride chemistry of Li and Ti provided initial conditions for leaching of impurity species from the sponge. Experimental results confirm that the effectiveness of leaching and removal of dissolved impurities from the sponge are dependent on leaching kinetics, which are influenced by temperature, particle size, and morphology. Of the variables tested, reaction temperature had the strongest influence on the oxygen content of the leached product. The HCl lixiviant concentration had a negligible effect under the conditions tested. Leaching of crude titanium sponge (−10 mm size fraction after crushing) at 14°C in either 1 M or 0.032 M HCl yielded a titanium sponge product that met the ASTM standard specification for commercially pure Grade 1 titanium, i.e., oxygen content < 0.18 mass% and chloride content < 0.15 mass%.

Dec 13, 2022

By REED H. HYDE

IN these days of low metal prices and difficult marketing conditions, any treatment that will improve the grade of a product is of interest, particularly when the operation involves little or no addition to the total cost and may even result in a marketable by-product. Such a&apos; combination of circumstances exists, in some cases, in the zinc industry, where it has been found that certain impurities can be removed from .the ore during the Dwight-Lloyd sintering operation, previous to reduction to metal. Consequently it is not surprising that zinc smelters having these sintering machines are paying particular attention to this phase of the operation. Loss of zinc as fume is very low under the conditions obtaining in sintering zinc ores, but impurities such as cadmium and lead are more readily fumed off and it is on this fact that the purification is based. As a result of preferential volatilization of these impurities a sintered product&apos; is made from which purer zinc metal or oxide can be produced, while the fume may be collected and treated to recover the impurity metals. To be effective the operation must be carefully conducted, but no special equipment other than that of a well designed Dwight. Lloyd plant is needed.

Jan 1, 1931

By Tilak Raj Mankhand, Mudila Dhanunjaya Rao, Kamalesh K. Singh

"Zinc dust is used for the removal of primary impurities by cementation from the zinc sulphate electrolyte before electrowinning of zinc. However, the industrial zinc electrowinning plants has been reported that the zinc dust consumption is in large excess than the stoichiometric requirement. In the present investigation, morphology of the zinc dust has been altered by ball milling and utilized for the cementation of cadmium, which is one of the major impurity and compared the change in the rate of cementation with original zinc dust. Initially, 325 mesh size zinc dust was used for the optimization of the excess quantity of zinc dust to be used at a temperature of 50 °C. The chemical analysis of zinc dust before and after ball milling and morphology were studied by scanning electron microscopy (SEM), and the solution was characterized by Atomic Absorption Spectrophotometer. The rate of cementation increased with increase in ball milling time. The residual precipitate obtained after filtration was also characterized by X-ray diffraction analysis. Finally experiments were conducted to study the effect of temperature and kinetics of cadmium cementation using first order reaction kinetics. Based on the integral method, the calculated activation energy for the cadmium cementation with 4-hours ball milled zinc dust was found to be 3.39 KJ/mole. INTRODUCTION Primary production of zinc in the world is carried out by hydrometallurgical route. The primary impurities in the neutralized zinc sulphate solution that cause negative effect on electrowinning are copper, cadmium, cobalt, and nickel. Copper diminishes the current efficiency and cadmium contaminates the cathode zinc (Morgan, 1977) while electro winning. Nickel and cobalt lead to perforation in the zinc deposit and prevents the electro winning process (Abrasheva et al, 1984). Due to higher electro positivity of these metal impurities than zinc, they can co-deposit with cathode zinc at the time of electrolysis. In addition to that, some possible impurities (including cobalt) in the electrolysis may lower the hydrogen overvoltage, allowing deposition of hydrogen at cathode resulting in fall of current efficiency. The deposition of zinc on the cathode is possible only at higher hydrogen overvoltage which is practicable in the absence of such impurities (Raghavan et al., 1999). Cementation is one of the prominent purification technique, and in that less reactive metal can be replaced by highly reactive metal by allowing them into precipitation. Cementation of cadmium from zinc sulphate electrolyte is being done by the addition of zinc dust."

Jan 1, 2018

By T. Bartnitzki, N. Fietz

"INTRODUCTION For a long time now automation has been state of the art in production engineering and chemical engineering. The advantages of automation are, for instance, higher reliabilities of production processes, higher product qualities as well as capacities and improved safety conditions for the personnel. In contrast, many operations in mining are still conducted manually by machine operators instead of autonomous control units. One example for this is the excavation of underground hard coal which is still executed with aid of human perception. The Institute for Mining and Metallurgical Machinery (IMR) has been working on possibilities for sensor-based automation of mining machinery for many years now. Thereto the focus is set on the implementation of common material analysis techniques into ruggedized conditions as a basis for automation. Laser-induced breakdown spectroscopy (LIBS) for instance is an atom emission technique which enables the determination of the elemental composition of a sample. After introducing LIBS this paper will give an overview on dust formation during the cutting process. With the illustration of a few examples the challenges in determining dust concentrations specifically such of cutting processes are explained in further detail. The final chapter will outlay the possibilities and challenges in utilizing cutting-induced dust for the automation of shearer loaders. LASER-INDUCED BREAKDOWN SPECTROSCOPY LIBS Fundamentals LIBS (laser-induced breakdown spectroscopy) is a contact-free method for analyzing materials in any state of aggregate. It pertains the atom emission techniques and is based on the generation of plasma, inducing avalanche ionization on the surface of a solid material or any spot in a gas or aqueous solution. With sufficient background information on the expected elements and an additional calibration, this method can determine all present elements not only qualitatively but also quantitatively. However, this method cannot be utilized for determining the molecular composition of materials – if this feature is required a complementary method such as Raman analysis needs to be added. (1, 2)"

Jan 1, 2015

By J Coveney, A Rich, D Grimsey, J Wood, S Creedy

In 2021, BHP and Metso examined processing of high-MgO nickel sulfide concentrates using Metso’s Ausmelt Top-Submerged-Lance (TSL) technology. Test work was conducted in Metso’s pilot test work facility in Dandenong, Australia to explore operability of the SiO2-FeO-MgO-CaO-NiO slag system across a wide range of compositions, temperatures and bath oxygen potentials. Pilot-scale testing aimed to define slag ‘operability limits’, representing the lowest bath temperature at which stable process and equipment operation could be maintained. This work was supported by FactSage™, version 8.2 (by Thermfact/CRCT and GTT-Technologies) thermodynamic modelling, slag viscosity measurements, physical characterisation of quenched slag samples performed by the University of Queensland and benchmarking of commercial-scale TSL nickel smelting operations. A wide range of slag compositions were examined, with Fe/SiO2 ratios varying from 0.4–1.1, CaO content from 0.8–7.0 wt per cent and MgO content from 6–19 wt per cent. Slag SiO2/MgO ratio, wt per cent CaO and matte grade were found to have the greatest impacts on identified operability limits. Operability limits were found to be influenced by both the solids content in slag and viscosity of the remaining liquid slag phase, with the relative contribution of these parameters heavily influenced by the slag composition. In the majority of trials, limits were defined by a theoretical solids content of 40–50 per cent, however in trials with a low Fe/SiO2 ratio and/or low wt per cent CaO, limits were characterised by a much lower solids content due to the increased effect of the liquid slag viscosity in determining the behaviour of these slags. The test work highlighted inherent flexibility of the Ausmelt TSL process to operate across a wide slag range of slag compositions and recover from process disturbances without an interruption to feeding. The trials also demonstrated the possibility for Ausmelt TSL technology to process concentrates with an Fe/MgO ratio as low as 1.4, which has important implications to the commercial-scale processing of high MgO feeds. Arsenic rejection across the trials was very good, with only 30 per cent of arsenic in the feed inputs reporting to the matte phase. Such high levels of arsenic removal provide the Ausmelt TSL process with a notable advantage over alternative smelting technologies.

Aug 21, 2024

By Gerhard Lang

"Slurry Microtunneling is a well-established technology building on over 20 years of experience in successful tunnel installations under all kinds of soil conditions across the U.S. and Canada. Recent microtunnel installations prove that initial hesitation, e.g. curved drives, is fading and long-distance pipe jacking projects as well as lake outfalls are being considered. One of the younger technologies is Direct Pipe®, which combines the benefits of HDD and Slurry Microtunneling. It fits exactly into the area where HDD is not feasible or too risky to apply. The paper points out the benefits of the Direct Pipe® technology for owners, engineers and contractors and discusses the latest developments of Slurry Microtunneling for long-distance, curved drives and sea/lake outfalls with wet recovery of the equipment such as on the ‘Keswick Outfall Project’ in Ontario. The first Direct Pipe® installation in the US was executed in August 2010. Since then, another 22 crossings have been carried out amongst a total of more than 60 Direct Pipe® crossings worldwide. INTRODUCTION Pipelines installed underground are indispensable for supplying the growing world population with water, oil, gas and electricity, for removing wastewater and for providing functioning telephone and communications networks. During recent years the limits of trenchless applications have been permanently shifted, leading to higher and more stringent project requirements and consequently new technologies, either as further development of existing methods, or through the development of new methods by incorporating elements of proven technologies. MICROTUNNELING TRENDS IN NORTH AMERICA Slurry Microtunneling has a wider geological application range in comparison to EPB and hard rock Microtunneling. The Slurry MTBM can be equipped with specific cutting wheels to cope with different soil conditions. The most flexible and most often employed type is the mixed soil cutting wheel, which contains a mixture of disc cutters as well as scrapers for varying soil conditions from cohesive soils (clay, silts) to highly permeable soils including sands, gravels and cobbles and even hard ground formations such as rock and boulders. A detailed geotechnical report provides the appropriate data to configure the MTBM and its features to the ground conditions expected. Mixshield or hydroshield (AVN/AVND) MTBMs in particular, can be safely operated with little overburden (~ 3-5 x machine diameter) and minimum risk of frac-out or settlement on the surface. This is especially beneficial in urban areas with sensitive buildings or for river crossings with protected fish habitats."

Jan 1, 2016

By R. J. Jewell

The storage capacity of any given tailings storage facility (TSF) is a function of the volume available for the tailings, for which the geometry of the final upper surface of the tailings is most important. One of the advantages that can be obtained from thickening tailings prior to discharge is that the tailings can be stacked at a steeper beach angle than is obtainable with conventional low-density slurries. However, there is at present no universally accepted method available for the accurate prediction of tailings beach slopes. This paper examines the current situation with the objective of putting the quest for a method for the accurate prediction of beach slopes into perspective. The paper references published reviews of the best-known beach slope prediction methods. However, there do not appear to be any independently verified projects or published references to projects on which a Class A prediction has been validated for any of these approaches, and in those instances where projects have been implemented correlation of actual with predicted slopes has been poor - often due to differences between the properties of the tailings assumed in the design and those actually achieved in the field. The author also concludes that flume-scale testing cannot be taken as a reliable indicator of full-scale performance, and suggests that the outcome of any current predictive method should be used by experienced practitioners as only one of a range of indicators in order to suggest a range of slope angles likely to result for any given operation. Practice has shown that it is possible to manipulate beach slopes by changes to the disposal technique, such as limiting the rate of discharge per discharge point and by increasing or decreasing yield stress, but the impact of these changes cannot readily be predicted. There are also newly emerging technologies, such as the injection of a polymer into the tailings at discharge, that will enhance the dewatering of tailings and hence expedite the consolidation of the tailings, that could well facilitate the development of steeper beach slopes. The overall conclusion is that with the current state of knowledge, the accurate prediction of beach slopes is not possible. Furthermore, in view of the inherent variability of the tailings parameters from any operation, it may well be of more value to concentrate on developing an understanding of the means by which the tailings parameters may be manipulated by the operators to achieve a given beach slope than to concentrate wholly on developing a generic beach slope prediction model.

Jan 1, 2012

By D. M. Lane, J. M. Berkoe

Engineers and Owners share a common desire to build reliable, efficient plants on schedule at reasonable costs. This paper describes one tool that Bechtel finds can integrate these objectives by “putting innovation into practice”. Examples of such innovative engineering practice include the use of computational fluid dynamics (CFD) to determine efficient designs. This paper outlines several examples of CFD applications on actual Mining and Metals Projects from around the world. The focus here is to highlight the modeling objectives, analysis strategy, actual benefit obtained from the work, lessons learned to improve future efforts and the common mistakes that can obscure the correct or best results, despite impressive graphics. The tools are powerful, and the results are more powerful when applied with skilled and well-directed human effort and ingenuity.

Jan 1, 2000

By J. A. Brusset

THE Greenhill mine of West Canadian Collieries, Limited, is situated at Blairmore, Alberta, and produces 2,500 tons per day of bituminous coal. On Monday, October 25th, 1943, smoke was discovered by a party of firebosses on their regular weekly inspection of air-ways. Probably the fire had been smouldering for several days but, as it had started on the outcrop at the top of an old raise filled with dirt, only a small quantity of smoke could filter through, and the plume of mist that crowns the fan at that season had prevented the fan-man from noticing it. This raise is only about 200 feet from the fan, and is 70 feet long between the fan-drift and the outcrop. It was impossible to prove the origin of the fire, as it had probably started several days before it was discovered, but it is possible that a careless smoker may have thrown a match into the opening at the outcrop, and that the old, dry timber had caught fire. The airways are in No. 2 seam, a bituminous seam 18 to 25 feet thick surmounted by shales and sandstones. Only 45 feet vertically above it is No. 1 seam, 12 feet thick, overlain by a strong conglomerate. In that vicinity, No. 1 seam had been worked out about ten years ago and the strata between the two seams are undoubtedly fissured. The pitch of both seams is 43 degrees.

Jan 1, 1945

By W Potma, C Brauhart, S Halley, S Urbisinov, A Scogings

Truly integrated, quantitative, 3D GEOmetallurgical (or mineral system) characterisation, classification and 3D modelling should provide a cradle to grave unifying link across the exploration and mining value chain. All too often, spatially representative (quantitative) characterisation and modelling of a mineral system is delayed until feasibility stage, incurring a significant opportunity cost. The application of robust GEOmet characterisation methods early in the project lifecycle (at exploration stage) improves ground selection, exploration, and Mineral Resource estimation outcomes, long before there is a need for metallurgical test work. The value of this early provision of quantitative 3D mineralogy models is compounded at project feasibility stage, and continues to accrue over the entire project lifecycle, delivering cost savings, improved decision making and early warning of issues and opportunities.CITATION: Potma, W, Halley, S, Scogings, A, Urbisinov, S and Brauhart, C, 2018. Putting the ‘GEO’ back in front of GEOmetallurgy: importance of early implementation of quantitative mineral system characterisation, classification and modelling, in Proceedings Complex Orebodies Conference 2018, pp 55–57 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Nov 21, 2018

By Edward L. Hajduk

During sonic logging quality control testing of the drilled shaft foundations for the replacement bridges crossing the Broad and Chechessee Rivers for SC 170 in Beaufort County, South Carolina, irregular signals were observed on a consistent basis near the shaft top elevations. These irregular sonic signals were attributed to access tube ?debonding?, which is the separation of the access tubing from the surrounding concrete. A total of 160 drilled shafts were installed for this project, of which 41 were evaluated using sonic logging testing. Both PVC and steel access tubes were used during the project to allow for sonic logging testing. This paper details the investigation of access tube debonding with time, discusses the solutions used to minimize access tube ?debonding?, and presents the results of the sonic logging testing for the entire project. The solution selected, installation of PVC along the pile length and steel access tubing within 40 feet from the top of shaft, allowed for reliable sonic logging to effectively evaluate the upper portions of the drilled shafts.

Jan 1, 2004

By Guy Borden, Michael J. Rzasa

Laboratory data on bubble point pressures and reservoir volume factors have been correlated as functions of solution gas-oil ratio, calculated gas gravity of the pentanes-and-lighter fraction of the entire fluid, differential residual oil gravity, and reservoir temperatures. INTRODUCTION Several correlations of crude oil properties have appeared in the literature. D. L. Katz4 in 1942 presented five methods of predicting oil shrinkage. these being of decreasing accuracy for decreasing amounts of information available. M. B. Standing- in 1947 published three correlations of laboratory flash vaporization data of California crudes. From values of GOR (gas-oil ratio), gas gravity, liquid gravity, and temperature, his correlations will predict bubble point pressure, formation volumes of bubble point liquids, and two-phase formation volumes. Curtis and Brinkley2 in 1949 presented several correlations. From the gas-oil ratio, an approximation of reservoir volume factor and barrels of condensate recoverable per barrel of reservoir space may be obtained; along with liquid gravity and reservoir temperature, the GOR will allow prediction of bubble point pressure. These last cor- relations seem to be more qualitative than quantitative. Generally, laboratory bottom hole sample tests furnish information on solution gas-oil ratios, residual oil gravities. bubble point pressures, viscosities of oils, liquid shrinkages, and occasionally gas gravities. Each of these data has its own applications and use in reservoir engineering calculations. The particular uses of correlated bottom hole sample data are found in (1 Providing a basis for obtaining estimates of formation crude properties in fields where bottom hole sampling is impractical or impossible. (2) Greatly reducing the time in obtaining the desired information. (3) Determining the applicability of the results from various bottom hole samples to particular field problems. (4) Avoiding, in many cases, the uncertainties of sampling by replacing it with an element over which greater control can be exercised. (5) Permitting use of preliminary field data in application of production procedures before a bottom hole sample can be obtained and analyzed in the laboratory. (6) Serving as a check on data which may appear out of line. (7) Estimating for a particular type crude the appropriate equilibrium constants by working backward from the bubble point pressure. (8) Estimating original or other past history properties of reservoirs that were not sampled in the past. PROCEDURE Application of the published correlations4,6 to Stanolind laboratory data indicated that the general scheme presented by Standing" could give dedrable results if changes were made in parameter positions and scales. The correlation curves were drawn with all the variables having consistent gradations except the temperature increments which were drawn in to best fit the data. The variables from available Stanolind laboratory data are defined below: (1) Gas-oil Ratio: Gas is liberated at reservoir temperature by differential vaporization (or rather by a series of flashes, approaching differential vaporization) and measured at atmospheric pressure and temperature, at which the compressibility factor is assumed to be unity. The oil is the residual liquid remaining after the pressure has been reduced to atmospheric. For the gas-oil ratio both volumes are corrected to standard conditions of 14.7 psia and 60°F. (2) Gas Gravity: It was decided to arbitrarily divide the hydrocarbons of the entire bottom hole sample into pentanes-and-lighter and hex-anes-and-heavier, and use a calculated gas gravity of the pentanes-and-lighter for a correlating variable. (Sample calculation is shown in Table 111.) (3) Liquid Gravity: This is the API gravity of the residual liquid from the differential vaporization. The gravity is measured at room temperature and corrected to 60°F.

Jan 1, 1950

By Harold Vagtborg

Equilibrium vaporization ratios were obtained for light hydrocarbons, nitrogen, carbon dioxide, and hydrogen sulfide in a reservoir fluid containing 35 mole per cent hydrogen sulfide. The data cover the range from 700 to 2500 psia at 154°F. The results of this study are compared with results obtained by other investigators on systems containing less hydrogen sulfide. When large amounts of hydrogen sulfide are present, the equilibrium vaporization ratios for ethane and heavier hydrocarbons are greater than the ratios for systems containing little or no hydrogen sulfide. Large amounts of hydrogen sulfide have the reverse effect on the ratios for methane. Routine PVT studies were performed on the reservoir fluid including flash and differential liberations of the dissolved gas. The pressure-volume relationships of the saturated fluid were also determined. It is shown that the use of published correlations on physical properties of reservoir .fluids can lead to gross errors when applied to systems containing large amounts of hydrogen sulfide. INTRODUCTION Equilibrium vaporization ratios for various components in naturally occurring crude oil and condensate systems have been reported in the literature.1,2,3,4 Recently, several papers have been published with emphasis on non-hydrocarbon components such as nitro- gen, carbon dioxide and hydrogen sulfide.5,6,7,8,9 The increased discovery of reservoir fluids having high concentrations of these non-hydrocarbon components, particularly hydrogen sulfide, has created a need for a further study of their phase behavior. Equilibrium vaporization ratios are known to vary with pressure, temperature, and overall composition of the system.&apos;" It was anticipated that ratios for systems containing large amounts of hydrogen sulfide would differ from the ratios for systems containing small amounts of hydrogen sulfide. Therefore, the present work was undertaken in order to obtain reliable equilibrium vaporization ratios for the reservoir-fluid in question. PROCEDURE The procedure followed was evolved after considerable experimentation on methods of handling the very sour crude. It was found that drying agents (e.g. CaCl2 and CaSO4) absorbed an appreciable amount of hydrogen sulfide from the gas used to prepare the recombined samples. The concentration of hydrogen sulfide dropped as much as 10 mole per cent in a single pass through a 3-ft drying tube. It was also found that when undried gas was agitated with mercury in the PVT cell, a black scum, believed to be mercuric sulfide, was formed and the hydrogen sulfide content of the gas dropped several mole per cent. Because composition changes during a run could not be tolerated, separation of the mercury and sour fluid was necessary. In order to effect this separation, a stainless steel piston, equipped with Teflon O-rings, was placed in the PVT cell between the mercury and the sour fluid. This piston had to be constructed in three parts because

Jan 1, 1955