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By Michael E. Stout

M.A. Industries, Inc. has developed and is now offering on a commercially available basis, complete systems to recover and recycle lead from spent SLI batteries. The system begins with the breaking and separation of the component parts of the batteries and subsequent treatment of the effluent water produced by this operation. The recyclable materials recovered from this process are metallic lead, lead paste and polypropylene. The lead paste is introduced into a process to convert it from a lead sulfate to a lead carbonate. The process also regenerates the salt solutions into reusable carbonate. The lead carbonate is then leached into an acid bath where it is later recovered by a proprietary electrolytic process. The metallic lead is recovered in a short rotary furnace producing metal for further refining and alloying. The polypropylene is further washed and then introduced to a reclaim extruder along with the proper modifiers and additives. The resulting resin can then be sold on the open market to injection molding processors. This complete system greatly reduces the amount of waste to be disposed of and completely complies with all applicable EPA guidelines.

Jan 1, 1993

By Richard A. Leiby

The recycling of lead-acid batteries in the United States has become a challenge as to how to balance ever increasing environmental regulation and cost with efficient operations. East Penn's captive secondary lead smelter has developed into a recycling facility producing lead, polypropylene, sulfuric acid, ammonium bisulfite, and non-hazardous discard slag. The emphasis has been to design a facility to comply with environmental regulations, to eliminate wastes, and to produce products, while at the same time, continuing to supply the company's battery manufacturing raw material needs.

Jan 1, 1993

By Ullrich Kammer

Metaleurop's secondary lead smelter at Oker produces 60.000 mtpy of lead and lead alloys. More than 8O2 % of the raw materials are spent lead acid batteries. The other 2O2 % consists of drosses, ashes, scrap lead, type metal, sludges, etc., and is processed in a short rotary furnace (SRF). Also, industrial batteries not fitting in the battery scrap treatment plant are processed in the SRF provided with gas/oxygen-burner. Till Sept. 199O2, a soda ash slag was used in the SRF-smelting similar to the rotary kiln-smelting at Oker. Facing the future problems of handling and dumping soda ash slag, Harz-Metall GmbH has improved SRF-smelting with a non¬hazardous slag, insoluble in water, easy to dump and cheap in fluxes. This slag is based on a CaO-SiO2 -Fe0-type. Aim of the slag smelting is to be within the temperature range of 2 1100° and 1200°C - the eutectic line of Olivine in the corresponding ternary system. Since Sept. 199O2 Harz-Metall GmbH has operated the SRF with an "Olivine-type slag" with good results. Although the material is a "leady" slag. HMG is optimistic of using it as a filling material for construction purposes.

Jan 1, 1993

By Chin J. Chang

Powder metallurgy (P/M) technique is known for its capability of producing near-net-shape parts. Its specific characteristics have resulted in low cost and eliminated of many secondary machining. However, more and more P/M parts do require additional operations to fulfil their complex geometric features and surface roughness. Many of the machining factors that influence the machinability of cast and wrought steel parts, such as cutting speed, feedrate, coolant, tool geometry and shape, are also considered in the machining of P/M components. The special feature in P/M structure is the porosity that can decrease the machinability and shorten the tool life. Different variables have been considered in the machinability of P/M materials. Densities and the free machining additive manganese sulphide (MnS), are the two main factors of material composition, which dominate the P/M machining performance. Machining process is the main method that generates the desired working surface of machining components. This paper will discuss the metallurgical structure of the powder metallurgy components, their physical properties and possible issues when encountering machining operation. Turning operation has been tested in this investigation to show the relationship between the cutting speed, federate, cutting forces and chip formation. This investigation also discusses how the free machining additive, manganese sulphide, affects the P/M structure and machinability in order to understand how the metallurgical structure can affect the machining operation and, how to obtain the optimised surface results.

May 1, 2001

By Charles E. Nelson

In considering the types of scrap that are processed into secondary magnesium, it is important to point out that the greatest proportion of this material is fabrication, foundry and machine shop scrap that is generated during the conversion of magnesium products into the finished article. This material, then, is largely of the same composition and quality as the original ingot or heat of metal except as it may be mixed with other compositions or metals in the fabricating process. Insofar as such materials can be processed back into secondary ingots or final products which meet the composition and property standards required of the original virgin stocks, then it seems reasonable that such products are fully equivalent to the primary products. With these premises then, it is the intent of the present discussion to consider briefly some of the methods whereby scrap may be generated, segregated, shipped, and processed in such a manner that the final products will be equivalent to virgin materials. Some information on the effects of impurities will be given in order to aid in the evaluation of these products. SCRAP GENERATION The method by which scrap is generated serves in a rough way to classify the resulting materials in terms of how they may be handled and recovered. These methods will be dealt with briefly. Machining operations such as milling and turning undoubtedly provide the great-

Jan 1, 1943

By R Austerberry, S Green

The discovery of the Cuffley Lode at Mandalay Resources Costerfield Operations provided an opportunity to extend mine life via mining the offset depth extension of the previously worked Alison Mine. Access from the existing Augusta Mine placed the initial Cuffley underground workings at approximately 250 metres depth from surface. As the new orebody transitioned towards production, a secondary means of egress needed to be established. The depth of the initial capital development presented a challenge in establishing a secondary means of egress that could be confidently relied on. The availability of land to locate a surface shaft collar further reduced available options and geotechnical drilling further limited suitable shaft locations. Time limiting factors such as permitting and having a secondary means of egress in as soon as possible, further highlighted that an innovative secondary means of egress was needed. A consideration of using an emergency gig lowered by a suitable sized crane supplied by an external crane contractor was investigated and found to be a suitable outcome. This Emergency Gig was deployed via the Cuffley Return Air Raise. When trialled, the emergency gig was found to provide a reliable, repeatable extraction method with an acceptable level of risk. Issues discovered during such trials further improved the process to a point where this extraction method became the adopted secondary means of egress for additional lodes that existed at depth. When assessing possible methods of secondary means of egress, the use of a third-party crane and custom designed and fabricated emergency gig should not be discounted. Where a crane can be sourced within an acceptable timeframe, the emergency gig extraction method provides a reliable safe and cost-effective means of secondary means of egress, especially when multiple shafts are to be developed. Local laws may negate the ability to employ such a system, although it is believed with good communication and well-constructed risk assessments, this system can be safely deployed.

Mar 15, 2021

By A. A. Novoselov, U. Kelm

"Large volumes of mine tailings accumulated in surroundings of porphyry copper deposits represent a growing threat to environment. They contain significant concentrations of toxic metal and metalloids which can contaminate river runoff, ground waters or can be transported by wind. Both extreme pH of fluids in tailings impoundments and high surface areas of processed mineral grains provide their increased reactivity. As a result, during only a few decades, As, Cu, and Mo can be mobilized, redistributed through the tailing column and accumulated through post-deposition leaching, evaporation and contamination with natural fluids. Those processes are reflected in the forming of secondary minerals. Gypsum, Fe oxides/hydroxides, efflorescent salts and clay minerals are typical alteration products in tailings. Here we present the results of reactive transport simulations implemented on the base of PHREEQC and SUTRA codes. The one-dimension model emulates the mass balance between rainfall, evaporation and subsurface runoff, the kinetically- and thermodynamically-driven dissolution of tailing minerals, advective and diffusive transport of tailing fluids, and precipitation of secondary phases. A typical tailing column is composed of four unequal layers with predominance of (i) evaporation, (ii) secondary mineralization above, (iii) below water table, and (iv) near the bottom of dump. Those horizons are characterized by contrasting pH, chemical composition and bulk mineralization of pore fluids, distinct accessibility of atmospheric oxygen and, as a consequence, distinct intensity of sulfide oxidation. The modeling and its verification on Chilean tailings impoundments reveal the complexity and high rates of secondary mineralization. The accumulation of toxic alteration products is controlled by fluid transport through the tailing column induced by both rainfall/evaporation and exchange with subsurface runoff. The geochemical modeling is a powerful approach which allows comparing the processes in tailing deposits produced by distinct flotation regimes and providing the long-term predictions of their environmental impact as well as identifying sectors of tailings for possible re-processing."

Jan 1, 2018

Secondary minerals are the result of a process of concentration and enrichment and are commonly richer than the primary minerals of the same deposit. Secondary ores that contain abundant sulphides are commonly distinguishable in the field from primary ores; this distinction is more difficult with ores that carry a small quantity only of sulphide minerals, and microscopical examination of the ore in thin section is advisable in all doubtful cases. It is frequently difficult, and in some cases impossible, to determine the primary or secondary character of quartzose gold ores. The safest guide is the presence or absence of gaseous or fluid inclusions in association with the ore minerals; such primary association coupled with a lack of traces of oxidation is indicative of primary origin. Any ore that carries traces of oxidation, such as iron stains, endritic oxides of manganese, kaolin and so forth must be considered to have been acted upon by surface agencies, and secondary enrichment must be suspected. Further examination, however, may indicate that the contained value is primary, and, therefore, persistent in its vertical distribution. The manner of occurrence of secondary minerals is frequently characteristic; secondary minerals, being due to the action of surface waters, are commonly found in cracks through earlier minerals, or as crusts lining vugs or surrounding nucleal masses, or in general, in some distribution later than and not conforming to the arrangement of the primary minerals. Secondary sulphides are often found as soft black pulverulent masses or coatings, although they frequently occur well crystallized or as

Jan 1, 1932

By C Gunther

Secondary minerals are the result of a process of concentration and enrichment and are commonly richer than the primary minerals of the same deposit. Secondary ores that contain abundant sulphides are commonly dibtinguishable in the field from primary ores; this distinction is more difficult with ores that carry a small quantity only of sulphide minerals, and microscopical examination of the ore in thin section is advisable in all doubtful cases. It is frequently difficult, and in some cases impossible, to determine the primary or secondary character of quartzose gold ores. The safest guide is the presence or absence of gaseous or fluid inclusions in association with the ore minerals; such primary association coupled with a lack of traces of oxidation is indicative of primary origin. Any ore that carries traces of oxidation, such as iron stains, dendritic oxides of manganese, kaolin and so forth must be considered to have been acted upon by surface agencies, and secondary enrichment must be suspected. Further examination, however, may indicate that the contained value is primary, and, therefore, persistent in its vertical distribution. The manner of occurrence of secondary minerals is frequently characteristic; secondary minerals, being due to the action of surface waters, are commonly found in cracks through earlier minerals, or as crusts lining vugs or surrounding nucleal masses, or in general, in some distribution later than and not conforming to the arrangement of the primary minerals. Secondary sulphides are often found as soft black pulverulent masses or coatings, although they frequently occur well crystallized or as

Jan 1, 1932

By E. Guerrini, M. Maccagni, J. Nielsen

"Lead is the most important material able to meet the current demand for energy storage. The lead acid battery is reliable, efficient and inexpensive. Continuous developments in battery construction are providing improvements in all aspects of the batteries’ performance. The lead acid battery is both the main lead product and the main raw material for lead production. More than half of the lead produced is from secondary smelters where batteries are the most important feed material. The environmental pressure on lead production has been increasing for many years, and continues to become stronger and stronger. The lead production processes and technologies themselves will require updating to meet the new regulations. Although they are very strict now, they will become even more so and current technologies may not be sufficient. Because recyclability is a strong point for the lead acid battery, the secondary smelters need to reduce the environmental impact as much as possible. In recent years, the secondary smelters underwent impressive changes in this direction, but some more improvements are possible. Electrochemistry can offer a step change improvement in making secondary lead production more environmentally friendly. Engitec has developed an electrochemical process base on a very high current density (high productivity) cell using an inexpensive electrolyte and at a relatively low cost. In this paper, the latest update on the technology is provided. INTRODUCTION The lead acid battery is considered the “walking dead” by some new technologies trying to replace it. It has played and will continue to play a very important role in our lives because it is inexpensive, fully recyclable and the existing lead and the mine reserves guaranty enough material for the extended future. According to the life cycle, the lead acid battery is the cheapest and the most effective system to store energy. Lead is practically a close loop where lead battery production consumes more than 80 % of the produced lead but contemporarily it is the most important raw material for the production of metallic lead. In fact, nowadays, the secondary production has overcome primary production and this trend is expected to continue. Primary lead is the make-up material for the existing battery production and the source of lead for the construction of the new ones."

Jan 1, 2018

By Ludwig Hermann

"Phosphorus is required by every cell of living organisms and essential for plant growth. It is a non-renewable resource that must be mined from natural deposits, going gradually into depletion. Abundant secondary resources are available in sewage sludge and meat and bone meal, with the highest exploitable P concentrations in ashes that remain from their widely used combustion with energy recovery. ASH DEC has successfully removed heavy metals and transformed sewage sludge ash into a marketable P fertilizer by application of a thermo-chemical treatment process. Pilot scale investigations in which ash was treated proved that generally heavy metal limits required by fertilizer legislation can be attained. To achieve a high P availability for crops – an essential fertilizer quality feature – was a more challenging R&D task. Our presentation demonstrates the scientific approach and R&D results that lead from assessment of market requirements to licensed products.IntroductionPhosphorus (P) is required by every cell of living organisms. It is one of the major elements for plant nutrition and therefore essential for crop production. P supply in plant nutrition depends entirely on external inputs into soils [1]. This is achieved by P-fertilizers deriving from rock phosphate deposits that are gradually going into depletion. Serious prognoses anticipate that rock phosphate will be the first low running resource in the world [2]. In the EU, last year 2.530 kt of phosphorus (P2O5 in fertilizers) was consumed and only 313 kt (P2O5 in rock phosphate) was mined. Since 2007, rock phosphate prices have increased by 500% because of a tight supply situation [3].For these reasons, P recycling is becoming an increasingly important issue. Suitable secondary raw materials with regard to their high P-content and abundance are sewage sludge and meat and bone meal. In the EU 989 kt P2O5 are accumulated annually in theses materials, of which 632 kt P2O5 are permanently lost to landfills and other forms of disposal. The main reasons for their limited recycling are concerns on heavy metal contents and organic pollutants that may incite health hazards. As an additional shortcoming, the availability of P from these materials to plants is poor and storage and transportation are problematic issues [4, 5]."

Jan 1, 2008

By G. W. Nabor, H. J. Ramey

A blotter-type electrolytic model was utilized to prepare flow diagrams for a field test of the in-situ combustion process. It is pointed out that the areal sweep of a combustion pattern is similar to sweep patterns that would be developed at an infinite mobility ratio, which exists (approximately) across a combustion front because of the complete removal of liquids from the sand behind it. The precision of the blotter method was tested by comparison with results obtained by other techniques and was found to be satisfactory. The blotter-type model will not furnish as much information as more elaborate and expensive potentiometric models, but its speed of operation and ease of construction make it a highly satisfactory tool to determine areal sweep patterns. A tabulation of sweep efficiency and mobility ratio is furnished for various well geometries. INTRODUCTION In connection with the first field experiment with the in-situ combustion method of oil recovery," flow diagrams for the unique well geometry and boundary conditions involved in the subject test were developed. From these diagrams, information concerning the areal sweep and distribution of flow was obtained. A survev of the literature on potentiometric models, utilized to solve two-dimensional flow problems,1,2,3,4,5,6,8,9,10 indicated that the information desired could be obtained by means of a blotter-type model by making certain modifications in the technique. The following discussion describes the application of the modified blotter-type electrolytic model to the solution of the problem of the flow of gases in an oil reservoir for an engineering appraisal of the progress of the combustion front during the first field experiment. Considerable information has been published on the theoretical aspects of electrical model techniques. One author stated that:' "The models are based on the observation that since the velocity of an ion in an electrolytic system is proportional to the potential gradient, just as the velocity of a fluid particle in a porous medium is proportional to the pressure gradient, the paths of the ions in the electrolytic systems must be similar to those of the fluid particles in a porous medium with the same geometry and equivalent boundary conditions." This suggestion of a real analogy has been established repeatedly by comparisons of analytic derivations with model results. The analogy between the movement of a combustion front and the model results is not as apparent, since the combustion process differs from water flooding and gas cycling in that the velocity of the burning front is different from the velocity of the injected fluid at the front in combustion. Analogy between electric current flow and movement of the burning front exists because the local velocity of the burning front is proportional to the air (mass) velocity at this point (assuming frontal temperatures are at least as high as the ignition temperature of the fuel). Most model studies fall into one of two categories: (1) electron conduction, or (2) ionic conduction models. Examples of these are models which employ as flow media either a thin metal sheet, or a porous blotter saturated with an electrolyte, respectively. Of the two, the porous blotter model, an ionic conduction model, appears to be the most adaptable to the flow problem that results when using in-situ combustion. This problem requires that the mobility of the particles in the model be controlled analogous to the mobility of gas flowing through burned sand of high permeability to gas and then through oil sand of lower permeability to gas. Although the blotter model has heretofore been

Jan 1, 1955

By John B. Campbell, George G. Binder, Loren H. Jenks

Conventional methods of producing crude oil generally leave in the depleted reservoir 1 to 3 bbl of oil for every barrel brought to the surface. This paper describes a field test which explores the possibility of using gas-driven liquid propane to improve oil recovery efficiency. Laboratory theoretical and experimental studies leading to the field test indicated that low residual oil values could be obtained using limited amounts of propane driven by gas. The field test involved (I) repressuring the reservoir to the vapor pressure of liquid propane, (2) injecting the liquid propane, and (3) injecting dry natural gas to drive the propane and oil to the producing wells. Considerable preliminary work, including new drilling, work-overs, and a pressure survey was necessary. During the test, oil production rates have averaged about nine times the final primary rates. The field average GOR is still below the pre-test value. Oil recovery to date is 112,000 STB. About one-third of the 143,-000 bbl of propane injected has been produced to date. Results of the C-2 block test are encouraging and larger, more definitive field projects ore indicated. INTRODUCTION The cost of finding new crude oil reservoirs continues to increase. Today the oil industry is drilling more and deeper wells and making fewer big discoveries. Nevertheless, the demand for oil and oil products increases each year. It is natural that oil companies, faced with this situation, concentrate on recovering more of the oil existing in our known crude oil reservoirs. There is room for much improvement. For every barrel of oil brought to the surface by present day methods of producing crude oil, generally 1 to 3 bbl are left behind in the depleted reservoirs. The "unrecoverable" oil in petroleum reservoirs is largely "trapped" by capillarity. Since flushing with a solvent is exceedingly effective in combatting oil loss due to capillarity, much effort in this direction has been made in recent years1,2,3,4,5. Liquefied petroleum gas (LPG) has been suggested as a relatively inexpensive. abundant, easily recoverable solvent for crude. Some operators have observed striking responses in oil recovery at production wells offsetting input wells in LPG storage reservoirs6,7,8. In spite of the low unit cost of LPG, however, it is uneconomic in general to inject a volume of LPG into a reservoir to remove a like volume of oil. A modification of solvent flushing in which a limited quantity of liquid propane is gas driven through a reservoir appears capable of recovering much more than 1 bbl of oil per barrel of propane injected. Also, most of the propane injected should be recoverable for sale or re-use. Since such a process could well have widespread and profitable application, The Carter Oil Co. is making an extensive evaluation of the technique's possibilities. Laboratory development of the gas-driven propane recovery technique was sufficiently encouraging to justify testing in the field. Since 1952, the Production and Research Departments of The Carter Oil Co. have cooperated in a field test in the C-2 Block leases of the

Jan 1, 1958

By J. G. Richardson, F. M. Perkins

Results and procedures are pre-cented covering a laboratory investigation of the effect of rate of water advance on the displacement of oil from clean water-wet sands. The experiments included water floods at atmospheric pressure with and without gas present over a range of flow rates from reservoir rates to rates ten thousand-fold higher. Water floods were also conducted at various rates at elevated pressure with no gas present. Other tests were made at elevated pressures by forming a free gas saturation by evolution of gas from solution in the oil before water flooding. Recovery of oil was found to be independent of the rate of water advance with or without gas present and independent of the pressure level of the water flood. A dimensionally-scaled model of a reservoir composed of a thick uniform sand was used to study the effect of rate on the tendency of water to underrun the oil because of the greater density of the water. Another model was used to study the effect of rate on the tendency of water to channel down the more permeable sand in a stratified reservoir composed of sands of diffierent per-meability in intimate contact. The effect of the presence of gas on the flooding conformance was studied with both models. The results obtained using these simple models provide a basis for predicting behavior in more complicated systems. INTRODUCTION In spite of the great amount of research on the flow of fluids in porous rocks, there still exists some disagreement as to the influence of the rate of water advance on the displacement of oil by water flooding. Various investigators have found that increasing the rate of water injection would decrease, increase, or have no effect on recovery of oil. One reason for this disagreement has been a lack of understanding of the effects of the capillary forces which influence the results obtained in the laboratory at low rates with short columns. Other causes of the disagreement have undoubtedly been inconstancy and uncertainty of the wetting properties of the porous media studied, inaccurate saturation determinations, and in some instances conclusions based on insufficient data. Capillary forces are involved in the displacement of oil by water in two ways. On the microscopic scale, the capillary forces control the dis- tribution of oil and water in the pore spaces of the sand. The magnitude of these forces is governed by the preference of the sand to be wet by water, the pore sizes and geometrical shapes, and the interfacial tension between the water and oil. On the macroscopic scale, differences in saturation at the flooding "front" when water displaces oil result in capillary pressure gradients. These gradients cause water to flow preferentially ahead of the front. In short laboratory columns at low rates, the front can span the entire column length. Also, at the outflow boundary the preference of sand to be wetted by water results in retention of water and a high water saturation in the region of the outflow face. This effect is commonly called the boundary effect.' The capillary pressure gradients which complicate the interpretation of flooding performance of short laboratory columns at low rates of water advance become negligibly small under certain conditions. The conditions where capillary pressure gradients are negligible are in long, homogeneous reservoir sands,' at high rates of water advance in short laboratory columns,3 and at any rate in laboratory columns as the residual oil saturation is approached. Thus, laboratory water floods, conducted

Jan 1, 1958

By T. M. Geffen, H. N. Hall

One-third to one-half of the original oil is left in most reservoirs even after thorough gas driving or waterflooding. In contrast, essentially all of the oil contacted con be recovered by flooding with a solvent (a fluid miscible with the reservoir oil). It is not economical to fill a reservoir with solvent since the value of the solvent would very likely exceed that of the oil. A practical method would be to inject a small bank of solvent to displace the oil. This solvent bank in turn could be driven through the rock by a less valuable scavenging fluid, such as natural gas which is also miscible with the solvent. Such a method of oil recovery was studied in the laboratory using long (up to 95 ft) core systems. It was found that, as the solvent moves through the reservoir, the front end of the solvent bank becomes mixed with the oil and forms a relatively short mixing zone between undiluted crude oil and pure solvent. An engineering correlation was obtained which can be used to predict the length of this zone. Displacement of the solvent by natural gas can be achieved with complete miscibility (above the critical pressure of the gas-solvent system at reservoir temperature) or with partial miscibility at lower pressures. Under conditions of complete miscibility, it was found that the length of the gas-solvent mixing zone could be predicted from the correlation developed for the solvent-oil mixing zone. With partial miscibility, two phases exist and the solvent is displaced by a modified gas drive in which vaporization and condensation occur. Equations are developed to predict the performance of this type of displacement. Two plans are suggested for application of miscible fluid displacement. one for miscible displacement of the solvent and the other applying to lower pressures where partial miscibility occurs during solvent displacement. Calculations based on the laboratory tests indicated that a bank of solvent with a volume of less than 10 per cent of the hydrocarbon volume under consideration will generally be adequate to obtain high oil recovery from the portion of the reservoir contacted in miscible fluid displacement. INTRODUCTION The conventional methods by which oil is displaced from reservoir rock—solution gas drive, conventional gas drive, and waterflooding—are all processes in which the oil is expelled from the rock by direct displacement with a fluid immiscible with the oil. Because of the immiscible type displacement, complete recovery of the reservoir oil is not achieved. In economically successful flooding operations, as much as 50 per cent of the original oil may be abandoned in the reservoir as unrecoverable. The use of a solvent (miscible with oil, such as LPG) as an injection fluid does not have the undesirable displacement features common to the use of gas or water (immiscible with oil). It can be readily appreciated, however, that it would not be economically feasible to displace the oil and entirely replace it with a solvent. A process was therefore devised for use in field operations in which only a small volume of solvent would be required to obtain essentially complete oil recovery in the portion of the reservoir contacted. In this process, the solvent acts as a buffer between the reservoir oil and injected gas, allowing the natural gas to displace indirectly the oil with much greater efficiency than if the gas displaced the oil directly. DESCRIPTION OF OIL RECOVERY PROCESS The solvent oil recovery process will be described in

Jan 1, 1958

By John C. Calhoun, J. E. Warren

A study of waterflood efficiency, given in terms of oil recovery at water breakthrough and u1timate recovery, has been made on short, consolidated Pyrex glass cores rendered oil-wet by chemical treatment. Contact angle. interfacial tension, permeability and porosity were the variables considered. Oil and water viscosities, core length and velocity of flooding were held constant. The data permit interfacial tension, contact angle, porosity, and permeability to be grouped into a scaling coefficient along with viscosity, velocity of flooding and length of core. Correlation of the .scaling coefficient with recovery at water breeakthrough is found to follow prediction; correlations of ultimate recovery demand a scaling coefficient different from that which correlates breakthrough recovery. The work indicates that, with proper control, a group of similar natural cores, of permeability plug size, call he correlated 10 indicate basic flooding performance. INTRODUCTION The fraction of oil recovered from a porous medium is related to both reservoir conditions and production techniques. An investigation of all factors that enter into this relationship is necessary in order to arrive at the optimum method of exploitation for oil reservoirs. To define this relationship, laboratory studies have been made by a great many investigators. However. an important obstacle arises if the results of these experiments on water flooding are to be applied to practice. Ditferences in behavior are to be expected between reservoirs of the dimensions encountered underground and those used in laboratory work. Factors which play an important role under laboratory conditions may be of no consequence in reservoirs. Laboratory operating practices generally differ from field operating practices. Thus. a mere understanding of the mechanism of the displacement of oil by water is not enough. It is just as necessary that the process be analyzed dimensionally to give continuity and validity to the conversion from laboratory to field. The theory of oil displacement that has come to be accepted by the majority of those who are associated with reservoir mechanics had its beginning in the work of Leverett¹ and Buckley and Leverett2. The banking of oil, observed by many previous workers, was described by the "fractional flow" and the "frontal advance'' equations. The validity of the Buckley-Leverett theory was substantiated by the experimental and theoretical work of Terwilliger et al³; moroever, the theory was extended by the introduction of the idea of a "stabilized zone" to describe the banking of oil. Levine5 showed that the Buckley-Leverett equations gave reasonable agreement between calculated and experimental breakthrough recoveries only if the capillary pressure and gravity terms were included. Rapoport and Leas1 investigated the properties of linear floods and showed that both breakthrough and maximum recovery are related to a "scaling coefficient'' derived from the Buckley-Leverctt equations. Jones-Par-ra and Calhoun6 presented another scaling coefficient which included both viscous and capillary variables. Such scaling coefficients should suffice to predicl waterflood efficiency. However, some experimenters report data which does not appear consistent with the healing coefficient approach. For example, Engelberts and Klinkenberg7 conducted an extensive series of experiments on a dimensional model which contained a

Jan 1, 1956

By J. L. Fitch, B. G. Hurd

The presence of gypsum in samples subjected to standard core analysis introduces serious errors in the measurement of water saturation and porosity. The magnitude of these errors, depending upon the type of analysis procedure used, has been evaluated experimentally and theoretically. Water-saturated pore volumes determined by vacuum distillation or retort procedures may be too high by as much as 48 per cent of the volume of gypsum present. The maximum error in this value determined by Dean-Stark extraction with toluene is 36 per cent of the gypsum volume. If pore space is measured by a Boyle's law type porosimeter the maximum erorr due to gypsum is 38 per cent of the original gypsum volume present. The conscientious core analyst may eliminate the errors caused by gypsum by either of two methods. He may apply suitable corrections for the water of crystallization removed from gypsum, or take special precautions to prevent dehydration of gypsum during core cleaning and alzalysis procedures. These alternatives are discussed and methods for obtaining reliable core analysis data are proposed. Gypsum (CaSO4 . 2H2O) occurs as a common mineral in many of the world's sedimentary basins. In addition to its presence as primary bedded evaporitic deposits, it is often found as secondary replacement zones and pore-fillings in host rocks. That it may cause false indications in porosity, both on neutron logs and in standard core analysis, has been generally recognized. False porosity interpretations from neutron logs result because the chemically bound water in gypsum attenuates neutrons as effectively as free water. Errors in core analysis result when gypsum is dehydrated prior to or during the analysis. Vacuum retort procedures used by many laboratories to determine fluid saturation and porosity effect a complete removal of water of crystallization from gypsum. The crystal water, distilled and collected with free water from the sample, is counted as water-sat11rated pore space. Dehydration of gypsum results in a decrease in volume occupied by calcium sulfate and a corresponding increase in pore volume. Thus, if gypsum is dehydrated by sample cleaning and drying procedures, subsequent porosity measurements with gas expansion or compression instruments will be high. The qualitative effect of gypsum on porosity determinations by retort procedures was discussed in a recent article by Bynum and Koepl3. They concluded that since false porosity was interpreted as being water saturated, determinations of oil content were not affected. Others in the industry, however, have pointed out that porosity values are often used with values of water saturation determined independently, e.g., from electric resistivity logs in making reserve estimates. Values of water saturation calculated from the formation resistivity using the Archie equation, S4= are actually low if values of are high due to gypsum. In this case, false porosity values due to gypsum could cause serious errors in calculations of oil-in-place. This investigation was made to determine quantitatively the effect of gypsum on porosity values determined by different core analysis procedures. EXPERIMENTAL PROCEDURES Dehydration of Gypsum The extent and rate of removal of water of crystallization from gypsum under conditions encountered in core analysis procedures were studied. Taken for the experiments were three types of relatively pure, naturally occurring gypsum, viz. selenite, satin spar and massive gypsum. Although all samples probably contained trace chemical impurities, each type lost the theoretical amount of water upon complete dehydration. An automatic recording thermobalance, similar to one described by Mauer2, was used to obtain dehydration rate data for samples heated in dry air. Water

By H. C. Johnson, J. K. Elliott

One of the primary requirements for successful operation of an enriched gas-drive project is to control the composition of injection gas. This can become a serious and difficult problem, particularly in cases where the enrichment material is being furnished from a number of field -produced gas streams. It is possible to effect control of the injection gas composition through frequent or continuous sampling; however, this can be extremely costly and, in many cases, impractical due to laboratory requirements of time. Another alternative would be to provide a calculation technique which would be flexible and sufficiently accurate to predict composition of the liquid and gas streams of interest at any point in the system. The purpose of this paper is to discuss a technique that was used successfully on an operating enriched gas-drive project for developing information which could be used for controlling composition of the injected gas. FIELD OPERATIONS The particular field (hereafter called Example field) in the example operation being discussed is composed of four oil reservoirs (A. B, C and E) and one gas condensate reservoir (D). Casinghead gas from the oil reservoirs and gas from the gas condensate reservoir are gathered through a field gathering system as shown in Fig. I for injection into Reservoir C. The gas mixture which is recovered from the five reservoirs for injection purposes is composed of gases liberated in 19 individual separators, each operating at a separate temperature and pressure. PROPOSED CALCULATION TECHNIQUE It is well known that vapor-liquid equilibrium calculations in general use throughout the petroleum industry can be used to predict reliably the phase behavior of hydrocarbon mixtures, particularly at pressures less than 1,000 psig. It is then a simple matter to account for the material on a ComPonent basis by m''ing flash and material balance calculations at each separation point in a hydrocarbon system. Accordingly, it was proposed to use vapor-liquid equilibrium and material balance cal- culations with a medium-sized electronic digital computer as a basis for developing a control procedure for use in controlling injection gas composition in the enriched gas-drive project. Although the approach is a simple one, the numerous vapor-liquid equilibrium calculations involved make the problem laborious; in this particular case, it would have been impractical to make sutficiently complete analysis without the aid of digital computing equipment. SAMPLING AND VERIFICATION OF CALCULATION PROCEDURE To obtain representative gas and liquid stream samples and to provide a quantitative measure of overall system Performance for comDarative purpLses, a thorough test of the field and plant system was conducted in the summer of 1957. Oil production at each battery was sta-

By Bruce F. Grant, Stefan F. Szasz

During 1947, a Sinclair research team was assigned to investigate thermal methods of oil recovery. The assignment was recommended by a survey of possible research approaches to increase the amount of oil that ultimately can be recovered from oil producing reservoirs. The use of heat to stimulate oil production rates by the melting of paraffin deposited in well bores can be traced back to within one or two decades of the drilling of the Drake well. The application of heat on a larger scale has been discussed by generations of oil producers. Shortly after the turn of the century, one intrepid operator is reported to have injected steam into a Pennsylvania property. After a few weeks, he apparently became discouraged and terminated his experiment. Subsequently, the literature contains references to several well-developed techniques for supplying heat to a producing well bore to melt paraffin or to reduce the viscosity of oil contained in the formation immediately around the well bore.1.?.3.4 Some early references discuss procedures to furnish heat to the reservoir,5,6 with the injection well as the heat source, thus obligating the process to maintain the entire rock mass at a temperature above that at which the desired improvement in oil recovery would occur. Another approach to reservoir heating was reported by a group of Russian technologists in 1935.7,8,9 They definitely demonstrated that combustion can occur within the porous structure of an oil-bearing sandstone. Their field experiments, however, relied less on combustion within the rock than on heat furnished by combustion of oil supplied to the injection well bore. Ignition of the air-oil mixtures in the well bore was found very difficult, and the field tests were carried on for only short periods of time. Publication of the Russian work spurred at least one independent operator in this country to try firing an air-gas injection well, on for only short periods of time. Publication of the Russian work spurred at least one independent operator in this country to try firing an air-gas injection well. The Brundred Oil Corp. reportedly obtained combustion in the sand immediately around the injection well bore, but the experiment was abandoned because of interference with normal production schedules. Injection capacity of the experimental well was greatly reduced by firing. The well was reshot and pieces of sand showing partial fusing of the quartz matrix were recovered. To the authors' knowledge no other field experiments utilizing combustion techniques for formation heating were undertaken prior to 1948, although the patent literature evidences continued interest in formation heating."'," CONCEPT OF COMBUSTION-SUPPORTED HEAT WAVE The references cited were in agreement that heat applied to a reservoir would increase recovery, but there

Jan 1, 1955

By J. D. Lindner, Gene E. Roark

Waterflooding operations in the Langston-Kleiner field. Young County, Tex., are described. Widespread application of formation fracturing has been practiced in both producing and injection wells. Field performance data arc cited which indicate than no detrimental effect on sweep efficiencies and that probable benefits in imectivily have resulted from the fracture treatments. I N T R O D U C I O N This paper is a report on a waterflood operation which is being carried out in the Lanpston-Kleiner field located in Young County, Tex. The oil reservoir aflected by this flood operation occurs in a Strawn sand member at an approximate depth of 3.550 ft subsurl'ace. The operators of' the project are Kleiner Estate. Turncr. Fiske. and West who are hereinafter collectively referred to as the Operators. Although the operation is unusual in several respects, the distinctive feature of this flood has been the widespread application of hydraulic formation fracturing treatments as a means to improve productivity and injectivity of the wells. It shall he the purpose of this paper to present basic information regarding the reservoir characteristics. op- craling practices, and waterflood behavior so that conclusions may be drawn concerning the effects which the fracture treatments have had on the performance of this water flood to datc. DEVELOP MENT Development of the 3,550 ft Strawn sand reservoir occurred during 1951 and 1952. The early development occurred on the Langston and Davis leases which arc in the northern region of the Operators' holdings and the wells were drilled on 20-acre proration units according to the field rules. However, studies of the economics of this program. coupled with the decision to proceed with pressure maintenance by water injection. resulted in the adoption of wider spacing in the later stages of development. This variation in spacing is apparent upon inspection of Fig. I upon which only the 3,550-ft Strawn sand producing and injection wells have been located on the Operators' properties. The development to the north of the operators leases is Ihe Garvey Strawn field and that to the south is the Taylor Strawn field. It wits determined that unitization of the leases to he involved in the waterflood program was not feasihle. Consequently. a system of offset injection wells, or lease line injection wells, was adopted from place to place as required to protect correlative rights in the program. This resulted in a dispersed array of injection and producing wells with relatively close proximity of wells along lease line areas and wider spacing toward

Jan 1, 1956