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By J. P. Timmons, J. H. Moran, G. K. Miller, M. A. Coufleau

A prototype equipment has been designed and built for the digital recording of well logs on magnetic tape at the same time that the regular film recording is made. The format of the digital tape produced is such that it can be used directly at the input of the ZBM 704, 7090 or other models of ZBM computers which accept digital magnetic tape. This apparatus has been used for the experimental field recording of dipmeter tape logs which were subsequently computed by means of an ZBM 704 or 7090. In this paper the equipment and the digital tape are described briefly, and their application to the computer-interpretation of dipmeter data is discussed. A principal element in the interpretation of the dipmeter log is the correlation of the three microresirtivity dipmeter curves to determine the depth displacements between them. Several correlation methods for computer use are considered, with particular attention to their sensitivity to error and their consumption of computer time. The tape data were used to compute information content of the dipmeter microresistivity curves in terms of their frequency spectra. The results show that the sampling rate used in recording the digital information is quite adequate and illustrate a use of the digital tape in evaluating the characteristics of new tools. Some examples of field results are shown. It can be foreseen that, when digital tape recording becomes available for general field use, a whole new realm of possibilities will be opened up for the processing of other well logs through computations, which hitherto were not feasible because they were too laborious and time-con.sunzing. INTRODUCTION The last few years have seen a revolution in the design and production of data-processing equipment. Stored-pro-gram digital computers have progressed from a research curiosity to the basis of a major industry. There are now hundreds of such machines in daily use in the United States. With the acceptance of a technique that was, in fact, already clearly described by John von Neumann in 1945, the last decade has seen great strides in the development'of components, reliability, programming systems and, most spectacularly, in the sheer number of machines built and in use. In 1957 there were enough digital computers available to the oil industry to justify the suggestion that it would be worthwhile to investigate the possibility of using these machines in processing well log data.' The first result of this investigation was the appearance of what may be referred to as the input-output bottleneck. Well logs are customarily recorded on film. To get these data into a machine required then (and still does): a time-consuming semi-automatic reading of the film; conversion of the log data to digital form; and recording these digital data in some medium acceptable for computer input, such as cards, magnetic tape, or punched paper tape. However, the recording, reading, and re-recording could only result in deterioration of the data. Therefore, it was concluded that the fist step should be the development of a new, more direct recording technique supplemental to the film recording, which would provide easy access to the digital computer. There are many solutions to the problem of recording log data in an easily recoverable form. After careful consideration it was decided to adopt the boldest solution which, it was felt, was also the most elegant. It was decided to record well logs directly, in the field, on magnetic tape in such a way that this tape could be used without further modification as an input to the IBM 704 or 7090 computer. To realize practical field recording of magnetic tape logs, it became necessary to develop in a rather small package, an analog-to-digital converter, a tape recorder, and the necessary multiplexing and control circuits to allow the simultaneous recording of a multiplicity of logging signals. The magnetic tape recording was to be made simultaneously with the conventional logging operation in such a way as not to interfere with it. Along with the development of hardware, it was necessary to begin development of interpretation techniques and machine programs that would exploit the power of the digital computer. Here, again, there is a long list of possible applications. After much consideration it was decided to concentrate on the interpretation of the dipmeter log as a first application. It is the object of this paper to describe in some detail the developments sketched in the last three paragraphs.

By J. A. Knox, R. M. Lasater, J. M. Tinsley

Chemical squeeze treatments have been used to provide temporary relief from certain production problems. The chemical fracture-squeeze technique, combining the effects of a fracturing treatment and a squeeze operation, has been more successful than conventional squeeze operations. Knowledge derived from well stimulation and reservoir engineering research provides a means for predicting the theoretical effective life of such a treatment. Analysis of theoretical equations and concepts developed allows selection of improved treatment techniques based on specific formation conditioins. Theory used in this analysis was developed as an extension of previous electrical model studies made to establish the expected flow and pressure profiles adjacent to a fracture system. The chemical fracture squeeze technique can be utilized in the economic application of corrosion inhibitors, emulsion breakers and paraffin and scale inhibitors. Application of this technique is shown to be effective. The slow return rate of injected chemicals, controlled by the resultant flow profiles and treatment variables, permits extended periods of chemical effectiveness. Results of field treatments are given, showing that the concepts outlined above for chemical fracture-squeeze treatments are valid and that applying this technique can help alleviate many current production problems. INTRODUCTION Much progress has been made in the last 10 to 15 years in developing chemicals for use in stimulating wells, maintaining production and protecting well equipment from damage due to corrosion. Not too many years ago, some wells seemed to dry up or wear out. In many cases the wells were produced as long as possible without any attempt at maintaining productivity. Even with the advent of new and better stimulation techniques, a rapid decline in production was observed. Methods of removing and, in some instances, preventing damage have been developed. Among thosc factors responsible for uneconomical production are scale, paraffin, corrosion, bacteria, water blocks and emulsions. Soluble scale-prevention chemicals have been developed1,2 that can be placed in a formation along with frac- turing sand. As the water produces back across this bed, the solid material dissolves slowly and can provide long-term protection from scale. However, bottom-hole temperature and salinity of produced water vary widely and both these factors influence the rate of solubility. Scale inhibitor composition is also a controlling factor. Some of the solid material may be crushed, increasing the surface area exposed to water and increasing the rate at which it dissolves. Some of the material may never be contacted by water and can be lost. However, this type of treatment has been very successful in many instances and has helped maintain economical production for extended periods of time. Liquid scale inhibitors, which are more widely applicable and more stable, have been developed in recent years; however, because they are liquids, their use has been restricted to treatment down the annulus, using metering pumps to provide proper concentrations in the produced fluid. This has prevented use in wells containing packers, in dually completed wells and in gas-lift and flowing wells. Wells that operate with an open annulus may also experience severe corrosion problems due to introduction of oxygen. Paraffin inhibitors3 have been developed that can be fractured into a well as particulate solids to be slowly dissolved in the produced fluid. These materials are not usually effective in wells with a bottom-hole temperature in excess of 120F since solubility rate may be too fast if that temperature is exceeded or if aromatic content of the oils is unusually high. Corrosion inhibitors have been developed that can be fractured' into a well for long-term feedback, but development of a material with proper solubility or feed rate has been difficult. Corrosion inhibitors are available in many different forms. Liquids have been lubricated down the annulus or sticks or pellets dropped down tubing. Inhibitor squeeze treatments5 devcloped a few years ago led to development of inhibitors with particularly strong film-forming properties.6,7 This technique basically involves displacing a highly concentrated solution of the inhibitor into the formation through the tubing. Kerver and Hanson8 studied the adsorption properties of inhibitors on various types of formations. They showed that, even though the inhibitor was displaced radially into the true permeability, it could be produced back for a long period of time because of slow desorption from the rock. Methods developed for monitoring the return of these inhibitors generally have established 1 to 6 months as the effective limit before retreatment is necessary.9 Inhibitors displaced into the interstices of the formation sometimes cause emulsions that either hamper production or cause treating problems on the surface.

By Oswald J. Heinrich

In the coal review for the United States for 1875, the Engineering and Mining Journal, January 1st,, 1876, remarks about the Richmond coal basin: "It has contributed but little to the supply of fuel during the year past, notwithstanding the fact that it is the most favorably situated of all our coal-fields, and possesses a fuel of good quality, well adapted to many important uses. An unaccountable lethargy seems to have fallen on all who have touched this field ; and yet, in the future it can scarcely fail to become one of the great sources of coal supply." In most respects indorsing the above remarks, I take occasion to lay before the Institute the following facts in defence of the Richmond basin; and not willing to criticize other mining enterprises in this field, I will make this one remark in general for all of them. While it is true that very little coal has been raised during the year in this field, it is equally true that even the little that has been raised could hardly be sold. When the output of the largest coal districts in the United States decreases, in consequence of the state of the market, it is not to be wondered at that the former small output of this basin dwindled down to almost nothing. But a far deeperseated evil, under which this field is suffering, may be discerned from the following remarks, which I hope will show that the latter part of the above remark in the Journal is not altogether fair. As the history of one mine in this district very nearly represents the history of the whole field, I will endeavor to give an account of the development of the Midlothian Mines, ranging amongst the oldest in the district, partially taken from a report of Col. Wooldridge, in 1811. Coal was mined in this neighborhood as early as 1700, and used (then so-called extensively) in the vicinity in 1775. A

By den Bulck A. Van

In Europe, 50% of the copper originates from recycling. High-Cu containing scraps are regularly rich in impurities like Fe, Ni, Sn and Pb. Many high-Cu containing scraps are fed directly into anode-furnace casting installations or furnaces with limited refining capability. The impurities levels of the anodes produced in these processes should however remain acceptable for further electro-refining. The distribution of Sn between copper and slag has been investigated for conditions relevant to copper converting. Unlike previous studies, this work focuses on the behavior of Sn relevant to fire refining conditions, which are essential for anode refineries.In this study, liquid Cu–1Sn and CuOx–FeOy–SiO2 slag, with CaO additions, were equilibrated at 1300 °C in vacuum sealed SiO2 ampoules. After metal–slag equilibration, the samples were quenched in water. The composition of the slag and Cu metal was investigated with Electron Probe X-ray Microanalysis. The distribution coefficients of Sn between slag and Cu metal were determined as a function of slag composition.

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-

On 23rd October, 1969, 54 members of the Institute set out at an early hour from Rand Airport in two chartered Dakota aircraft for a visit to the Hendrik Verwoerd Dam site. The weather was at the start rather unpromising but after passing Bloemfontein the overcast cleared and it turned into a glorious day for a most memorable visit. The Institute is indebted to U.C-Dumez-Borie Dams Limited, the main civil engineering contractors, and Mr J. D. McNamara their executive manager, for the very excellent arrangements made for this excursion. From the time the aircraft landed till a slightly belated departure the organisation of the extensive tours arranged for the parties was quite outstanding and a matter for congratulation to all concerned. At each of the many places visited there was a senior official to give an authoritative and comprehensive description of the work under his control. In addition the guides on the buses, loaned by the Department of Water Affairs, kept up an interesting running commentary throughout the day. A further much appreciated facet was the introduction of many of the experts on the site and a brief talk by each after an excellent lunch served at the recreation club. Each visitor also received a brochure with a progress report and a detailed site plan, with various sections highlighted in colour, and obviously prepared at the cost of much time and effort. The visit included tours of the large dolerite quarry, where some 150 000 tons of rock are removed each month, the 42 in. gyratory primary crusher, the secondary crushing and screening plant, the rod mill plant for sand production, and the automated blending and concrete batching plant. The transport of mixed concrete by 'silobuses' to the 6 cu. yd buckets of four Blondin cableways, two of which are radially movable and two with buffing towers, and the placing of the concrete in the huge blocks of the wall was watched from a vantage point. The most interesting part of the visit was without a doubt the inspection of the wall itself and the explanations of the many intricasies of its design and care in construction, covering aspects such as positioning of galleys, interlocking of blocks, reinforcement, refrigeration, actual concrete placing, subsequent grouting, etc. Other points of interest were the very complicated design of the wall itself, the river diversion plans, with three stages of coffer dams, the spillways, and the very well cut penstock tunnels.

By C. Scala, F. Bernstein

General expressions are derived relating the streaming potential to the electrochemical potential of a permeable junction separating two electrolytic solutions. By the methods of irreversible thermodynamics, these potentials are related to the flux of mobile species arising from differences in pressure and chemical composition. The flux is conveniently expressed as a transference number, the equivalents of a mobile species transferred through the junction per faraday of electricity. At constant pressure, the flux equation gives the electrochemical potential across the permeable junction. The streaming potential across the junction is obtained by imposing the condition of constant chemical composition. The familiar expression for the borehole SP is shown to be a particular solution of the general flux equation. The derived exprersions were verified in experiments with seven shale samples. Both the theory and experimental data provide additional proof of the presence and magniturle of the streaming potential in shales. INTRODUCTION In the interpretation of electric logs, there has been much concern over the correction to be made to the recorded SP for an electrokinetic or streaming potential originating from the difference in pressure between the mud column and the formation. It was long recognized by M. R. J. Wyllie that such an electrokinetic potential source mas in the mud cake opposite permeable sands.' More recently, M. Gondouin and C. Scala2 showed an additional but opposing electrokinetic source of potential to be in shale beds. Their work was supported by the very extensive and excellent work of Hill and Anderson.3 n the present contribution, the general relationships between the electrochemical potential and the corresponding streaming or electrokinetic potential are examined and clarified. A notable advance towards understanding the relation between the various sources of electrical potential in a borehole has been the application of the now common methods of irreversible thermodynamics to describe the passage of ions and water through charged electrolyte junctions such as in shales.' The advantages of these methods are twofold. Unlike classical thermodynamics, they can be applied to non-equilibrium sys- tems, i.e., systems in which flow takes place, provided the flow processes have reached a steady state. They also permit conventional thermodynamic properties to be related to the steady-state dynamic properties. These methods arc used here specifically to derive expressions relating the potential behavior of shales in terms of ion and water transport. Experimental verification of the expression for the shale streaming potential is given which in turn offers theoretical support to the existence of a streaming potential in shales.' Importantly, the relative contribution of transport parameters to the SP is clarified. The theoretical treatment is essentially that of Lori-mer, Boterenbrood and Hermans3 ut has been extended to derive the general expression for the SP.

By S. Gallagher, A. G. Mayton

Back injuries account for a high proportion of lost workdays in the mining industry and are a leading cause of disability in mine workers. Two risk factors for low back injuries are manual lifting and whole-body vibration exposure when operating mobile equipment. Recent research has shed light on possible mechanisms through which low back injuries may occur, and the results of these studies can be used to improve the design of lifting tasks and seats to decrease injury risk. This article discusses recent research results and how this knowledge can be leveraged to reduce the risk of low back pain.

By Jeff Kravitz, John Kovac, Wayne Duerr

Since 198 1, Federal mining law has required every miner working in underground coal mines to have a self-contained, self-rescuer (SCSR) available for use in emergencies. Some miners that have escaped from fires using SCSR's have reported that they had to remove their mouthpiece to talk during escape, thus compromising the protection afforded by the SCSR. If miners are in thick smoke during an escape, they may have trouble if they become separated from their group. The visibility can be so poor that separation can occur at very short distances. To address this problem, two-way, FM radios were built into the SCSR to improve the ability to communicate should the miners be separated over relatively short distances. The SCSR prototypes built and used in testing included both two-way radios and improved mouthpieces. Comparison studies were conducted using combinations of the new and old mouthpieces, and trials using the radio or not using the radio. Subjective judgments indicate that communication ability was significantly improved using the prototype devices. Communication problems have been encountered with teams using standard voice- powered communications systems. Mine rescue teams perform rescue and recovery work under extremely hazardous conditions, life lines are a standard part of mine rescue team equipment. Leaky feeder and quasi-leaky feeder life line communications systems provide significant improvements over standard systems. These improved systems allow all members of the team to communicate with each other and their base of operations. These innovations will significantly enhance the safety of mine rescue operations.

By Peter J. Nicholson

During my more than 40 years in the practice of underground construction and engineering, the industry has seen progress from the dig down to rock or hardpan or alternatively drive concrete or steel into the ground and count the blows; then you can be sure of you have a solid foundation; to the modern day, I?m willing to try anything to save money. Of course these are both exaggerations, but not gross ones. After getting bored being supervision on jobs counting blows, I struck out into the new field of ?tie-backs? as they were called in the United States, or ?ground anchors? as they were then termed in the United Kingdom. After installing some of the first permanent ground anchors for the Corps of Engineers on Lake Michigan as well as the highest loaded rock anchors of the time at two dams on the Ohio River, we were at the top of our game in the 1970?s. Subsequently in the 1980?s when my view of the future of ground anchors saw their installation becoming a commodity item, we branched out into ?Pin Piles? now known as Micro Piles, high capacity, steel tube encased, small diameter (5-12? or so), high capacity (100-500 tons) piling. Next came soil nailing, both temporary and permanent retaining walls, as at Cumberland Gap Kentucky. My next morph was into ?Cement Deep Soil Mixing? earlier on, known simply as ?soil mixing?. For this education I traveled to Japan several times and established a long-term, Joint Venture, relationship with one of the better known Japanese specialty ground modification companies. In Boston at the ?Big Dig? we established the then record size soil mixing project, 500,000 or so cubic meters of CDSM concluding in the year 2000. Since then I?ve been involved as a consultant mainly for dams and levees. Below is the story of how I came to be at this place in the road to innovation in Geotechnical processes.

By D. A. Hill

This volume contains a summary of the results of past analyses on U.S. Bureau of Mines Contract No. H0122061 which are relevant to electromagnetic location in mine rescue situations. The analytical results indicated that detection of a trapped miner equipped with a special transmitter is feasible in most situations. Location of the miner by surface measurements is also generally feasible within certain errors. The feasibility of miner detection and the accuracy of miner location have been examined theoretically for a wide variety of situations. Agreement with experimental results is generally good in cases where measurements are available.

By Hunsoo Choi, Sang-Mo Koh

Manganese nodule, the aggregate of fine grained manganese oxide minerals, is very brittle and fragile. In exploitation of manganese nodule, manganese nodules are easily broken into small pieces or powder during collecting and lifting from the sea floor. The broken manganese nodule under few millimeters and bottom sediment pumped up with manganese nodule affect to the lifting process. In this study, we tried to understand the physical properties of the powdered manganese nodule and bottom sediment, and to know the effect which may be rised to the actual mining of manganese nodules.

By Chris P. Pistorius

Over the past few decades the carbon intensity of ironmaking and steelmaking has been reduced considerably through improved efficiency in blast furnace ironmaking, partial replacement of coke with less carbon-intensive fuels, and increased use of scrap and direct-reduced iron in steelmaking. To evaluate possible further reductions in carbon intensity accurate process information is needed. A preliminary test of the fidelity of publicly reported data as a source of process information is reported here. The sources are industry roundups of electric furnace furnace steelmaking and blast furnace ironmaking (published by the Association for Iron and Steelmaking Technology), and data recorded by the Environmental Protection Agency under the US Greenhouse Gas Reporting Program. From a comparison for an integrated steelmaking plant and an electric furnace furnace plant, it appears that the values from the two data sources are consistent. The comparison does rely on process details such as the quantitative relationship between injected oxygen and carbon emissions in electric furnace steelmaking.

British Mining Fields, by J. E. Metcalf. Published by the Institution of Mining and Metallurgy, London, 1969. Price 50s. (Students, 30s.). A 100 years or so ago Britain's mining industry led the world in the production of coal and base metals. Although she still maintains a sizeable-and, under the circumstances, remarkably progressive-coal mining industry, her production of most other base minerals has long since been dwarfed by mining fields in the Americas Africa, Australia and the U.S.S.R. Nevertheless the story of mining in Britain is of wider interest than the present scale of operations there might suggest, if only because the domestic British mining industry has in terms of finance, technology and manpower been the fons et origo of many highly productive mining fields outside Britain, including the Witwatersrand goldfields. British Mining Fields was published by the Institute of Mining and Metallurgy to give delegates attending the Ninth Commonwealth Mining and Metallurgical Conference a succinct account of mining in Britain. The main emphasis is on underground mining of base minerals-treated regionally-with separate chapters on coal and gypsum. The author strikes an admirable balance between historical aspects, geological origin and environment of ore deposits, mining methods and economic factors, and provides a few key references for those who wish to make deeper studies. This is exactly the sort of booklet one often wishes were available on South African mining.

By A. B. Hildebrandt

P. B. Baxendell is to be complimented for an exccllent piece of work. To our knowledge there has been no previous publication of field data on the flow of oil and gas through the annulus of a well. It is certainly gratifying to see this work on annular flow confirm the previous published correlation procedure on tubing flow. It extends considerably the range under which reliable gas-lift calculations can be made. Baxendell discussed this work with us about a year ago and was kind enough to send a large scale plot of his correlation. We had been designing gas-lift installations on flow through the annulus, assuming that the original correlation of the f factor based on tubing flow' was valid as long as we stayed within the same mass velocity range on which the correlation was based. Doing this work necessitated the use of an equivalent diameter for the annular flow. The equivalent diameter is defined as area' of stream cross section wetted perimeter and for the case of an annulus is D, — D,. Substituting this in the basic equation correlating energy loss along with the area to flow required to convert the velocity, to volumetric flow rate, D (Baxendell's Eq. 7) becomes dell's expression, D,). Similarly, the D in 1.4737 X 10 (M&/D) becomes (D, + D;) for annular flow. On receipt of Baxendell's data, we. of course, recalculated it to put it into the form we were using, and to see how well it agreed with the correlation based on tubing flow. Fig. 1 shows the results, which were certainly gratifying. For low values of (D, - D,) pv, the data coincide with the data on flow through tubing, whereas at high values the data on flow through the annuli appear to be leveling off to a constant value. For very high rates of flow where the turbulence is very high, one might expect the value f to level out and become constant. A bulletin published in 1914 by the U. of Wisconsin presented results of a large number of laboratory teats in air lifting water through short lengths of 1.25-in. tubing. It was possible to correlate a random sampling of

By Gerrit V. R. Goodman, Jeffrey M. Listak, John A. Organiscak

Data on dust control practices, geology, and occupational exposures were gathered for approximately eighty underground continuous mining units. Despite silica contents in excess of 5%, nearly forty units successfully maintained silica concentrations at or below 100 µg/rn3 on a majority of occupational dust samples while the remainder had difficulty maintaining this level. These two sample sets were termed group A operations and group B operations, respectively. Analyses of productivities, geologies, and dust control parameters revealed only minor differences between these two groups. Subsequent analyses of face ventilation design showed considerable differences in silica exposure and silica content between group A and group B at the continuous mining machine and roof bolter operator occupations. These differences were minimal when using exhaust curtain ventilation with a dust scrubber', This face ventilation system may benefit operations having difficulty controlling silica dust exposure and silica dust content. Finally, the collected data showed that occupational samples from group B operations possessed generally higher silica exposures and silica content than similar samples from group A. The single head roof bolter (helper) possessed among the highest silica exposures and silica contents in both groups.

By James R. Means, George Bowser

A new phone system was developed that provides eight full duplex communications channels over a single twisted shielded phone line, with no central switching station or line amplifiers. This system greatly simplifies installation and maintenance over that required with conventional switching systems. The system is based on microprocessor technology and digital frequency synthesis. Frequency division multiplexing is used over a bandwidth of approximately 300 kHz, and a baseband voice channel (compatible with conventional pager phones) is provided as a backup to assure communication if the multiplex features fail. Multiplex operations are controlled over a 30-kHz digital channel. The system is designed to operate with up to 16 km (10 miles) of cable plant and a maximum phone separation of 8 km (5 miles). The digital techniques permit a limited amount of monitoring and control capability to each phone. This consists of two pair of contact inputs or outputs, to be used as desired. These "flags" may be read or controlled by a dispatcher's phone.

By P. Kerr

Iron segregation is pre-dated by copper and nickel segregation processes for which the experimental methodology and reaction chemistry were established. The accepted reaction sequence for segregation involves the generation of hydrogen chloride, the chloridization and volatilization of the metal chloride, and precipitation of the metal from the metal chloride in the vicinity of carbon. Iron segregation roasting offers a potential extraction solution for processing oxide deposits with complex mineralogy or waste streams such as Minette-type iron deposits, nickel laterites, ilmenite, red mud, electric arc furnace (EAF) dust, mill scale and slag. After subsequent magnetic separation, one is left with a high grade metallic iron powder which can be marketed for powder metallurgy or briquetted to serve as a direct reduced iron (DRI) product. The non-magnetic product is typically concentrated oxides including rutile, alumina, or oxides of V, P, and rare earths, etc. that may be economically recoverable with subsequent processing. While operating conditions vary for different metals, they share the requirements of an elevated operating temperature and a mixture of oxide ore, carbonaceous additive and a chloride additive in varying amounts all in a closed reactor to allow for reducing conditions and contain the volatile chlorides. This process is then followed by some form of physical separation. Testwork performed by the authors shows promising results that may aid in future development of the process. Segregation roasting of iron will likely never displace traditional beneficiation and ironmaking technologies; however, it has great potential in niche markets where traditional technologies have failed or current technologies generate substantial waste.

By J. S. Hegwer, P. M. Dunlap

An improved acid for the treatrrzent of sulfate-con-raining limestones and dolomites is described. The acid is designed to reduce he reprecipitation of dissolved calcium sulfate and the possibility of plugging permeable flow channels. In addition, this improved acid has a much lower reaction rate than that of regular acid; the advantages of a "retarded" acid are obtainable. Field testing of the acid has shown it suitable for use in sulfate-containing formations. Substantial improvements in productivity generally resulted. INTRODUCTION Acid treatments of limestones, dolomites and other formations bearing carbonate deposits are frequently unsuccessful when the calcareous formation contains sulfate, either as anhydrite (CaSO,) or gypsum (CaSO4. 2H2O). Preliminary dissolution in acid followed by redeposition of calcium sulfate appears to be a major factor contributing to poor well performance after acidizing. The precipitate is usually the gypsum form of calcium sulfate, but in higher temperature formations it may be anhydrite. The freshly precipitated crystals are nearly always very small and needle-like. They may occupy a gross volume many times that of the original anhydrite crystals and will obviously constitute an impediment to flow through newly enlarged flow channels. It is believed that the redeposition problem is most severe when anhydrite lines the fracture systems and large pores which supply the effective permeability of a formation. Microscopic inclusions of calcium sulfate also present large sulfate surface areas for dissolution in acid. In either case, great amounts of calcium sulfate may dissolve before the acid can be spent on formation carbonates. For regular spent acid (originally 15 per cent hydrochloric acid) the precipitate could be as much as 270 Ib gypsum/1000 gal acid. Two techniques have been applied by the industry for reducing sulfate plugging during acidizing. The method'.' commonly employed in the field is the attempted removal of a quantity of regular treating acid before it has reacted completely with the formation. This is practiced because the solubility of calcium sulfate is greater in a solution that is still acidic than in one which has been largely spent on the formation rock. The chance of precipitative plugging is therefore reduced if the withdrawal is successful. However, it is often impossible to get the acid out of the formation before precipitation occurs. A second possible method, which at first glance appears practical, involves addition to the acid of sequestering agents which form strong soluble complexes with calcium ions. These chemicals do increase the "solubility" of calcium sulfate in fresh acid, but to a lesser extent in spent acid. The sequestering agents have, therefore, proved unsatisfactory because the amount of sulfate eventually deposited from the spent acid may be greater than that from regular acid. Another logical approach to the problem of calcium sulfate reprecipitation is the prevention of the initial dissolution of calcium sulfate by the common ion effect. This may be accomplished by adding a soluble calcium salt to the fresh acid. The use of calcium salts in treating acids is not entirely new. An earlier suggested use of a soluble calcium salt in hydrochloric acid apparently failed to recognize the full extent to which the solubility of calcium sulfate could be suppressed. The present study extends this earlier work and adds certain improvements toward the development of a practical anti-anhydrite acid. LABORATORY DEVELOPMENT Calcium Sulfate Solubility Table 1 shows the results of a laboratory study performed to establish the effect of calcium chloride concentration on gypsum solubility. Because of the strong tendency of calcium sulfate to form supersaturated solutions, accurate solubilities are difficult to determine. These solubility data probably are reliable to within ± 15 per cent. The solubility of calcium sulfate in 15 weight per cent hydrochloric acid increases with increasing temperature. This trend is also followed in hydrochloric acid which cantains calcium chloride. This is contrary to the solubility behavior of calcium sulfate in water, wherein the solubility decreases with increasing temperature.