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By Bo Yan, Jiaquan Zhang, Haibo Sun

"Based on the validation of steady-state isothermal mathematical model by a 0.4-scale water model for the single-strand slab casting tundish, the effect of varying pouring temperature on the flow, temperature field, and residence time distribution(RTD) of the liquid steel was studied by a transient hydrodynamic model. Due to the decreasing temperature of ladle stream over a casting period of 50 min, the direction of vortex flow at the downstream side of dam changes to clockwise from the anticlockwise at 4 min after the new teeming, and reverts to anticlockwise direction again at 43 min. Meanwhile, the melt flow state in the dam hole is also varying with time. For conventional isothermal water modeling, the RTD parameters obtained are much different as compared with the non-isothermal ones. For the flow control devices(FCD) design, however, the identical optimal scheme can be concluded from the point of view of isothermal modeling.IntroductionOriginally, tundish was adopted as a buffer and distributor to hold and allocate molten steel for sequence casting upon ladle exchange and to provide a desired steel flow rate to the mould below. With the increasing demand to strand quality, the tundish has become a critical metallurgical reactor to enhance inclusions removal, avoid reoxidation of molten steel, and prevent slag entrapment. The general trends to obtain these metallurgical effects are to optimize steel flow pattern and to extend the residence time of molten steel in the tundish through increasing the volume of tundish and/or using FCDs in the interior of the tundish."

Jan 1, 2012

By Zhenzhou Yang, Zuotai Zhang

In the present study, we proposed a method that using sewage sludge (SS) as alternative fuel and raw material to produce cement clinker. It was found that the increasing amount of SS can favor for the formation of tricalcium silicate (C3S) but the excessive amount can cause the impediment effect. Furthermore, SS contains high contents of trace elements, especially for zinc and manganese. The thermodynamic equilibrium calculation of Zn and Mn are also conducted to further understand their transformation behaviors and the results show that zine is predicted as a volatile element while manganese shows great condensed potential during the cement clinker calcination process.

Mar 1, 2017

By E. D. Calvert

The objective of this research was to examine variations in melting and forging practice for four titanium-base alloys and to determine their effect on the resultant product. Of particular interest was the evaluation of the skull-casting technique. The data should serve as a guide to producers and consumers of titanium products. Physical properties of four titanium-base alloys in ingot form and in sheet form were evaluated and correlated, where possible, with variations in the melting and casting procedure. Consumable-electrode melting was used throughout, but arc current and furnace backfill pressure were varied, and ingots were formed both by melting directly into a water-cooled copper mold and by skull melting followed by pouring into a graphite mold. Alloying metal additions for the alloys tested were (1) 8 percent manganese, (2) 6 percent aluminum and 4 percent vanadium, (3) 6 percent molybdenum and 2 percent aluminum, and (4) 16 percent vanadium and 2.8 percent aluminum.

Jan 1, 1962

By Balladares V. Eduardo

Most of the arsenic contained in copper concentrates is removed in the gas phase during the smelting and converting processes and, according to recent environmental regulations, it is required to fix it in a solid stable form. In this regards, ferric arsenate has been reported as thermal and aqueous stable compound. Therefore, various alternatives for treating gas containing arsenic were considered in this work. From data obtained at laboratory scale on fixation of arsenic using iron oxide, a new process to treat copper concentrates containing arsenic was evaluated. The effect of temperature, oxygen potential and the sample porosity on the fixation of arsenic contained in a gaseous stream was studied, and the iron oxide converted into ferric arsenate was up to 10%. The obtained results suggest a new alternative for gas treatment with an interesting and attractive technical development. The arsenic was retained as ferric arsenate with thermal and aqueous stability, and it allows a safe disposal keeping the environmental restrictions. The kinetics parameters are used to scale up laboratory results to higher processing rates.

Jan 1, 2005

By Albert R. Ledoux

I AM indebted to The Kaolin Co. of West Cornwall, Conn., and particularly to its engineer, Mr. M. Wanner, for permission to make public, through the Transactions of the American Institute of Mining Engineers, the interesting results of his experiments, having in view the winning of kaolin from deep deposits without shaft-sinking or removing of the overburden. So far as I am aware, nothing like it has been accomplished heretofore, although it reminds one of the methods successfully employed in Louisiana for the winning of sulphur from deep beds by the sinking of pipes one within another, injecting superheated steam under pressure through one pipe, the heat of the steam liquefying the sulphur and the pressure forcing it up through the other pipe to bins at the surface. The kaolin-deposit at Nest Cornwall is an alteration in situ-that is, it is not sedimentary. A series of clay-veins dipping about 500 from the vertical, lie between a foot-wall of limonite and a hanging-wall of gneiss and hornblende schist. The clay-veins alternate with veins or seams of more or less broken quartz, and unaltered feldspar. The deposit, which occurs at a point about 600 ft. above the Housatonic river, was opened five years ago, and about 5,000 tons of a superior grade of washed kaolin has been extracted from open pits and sold. It soon became evident that this node of extracting the product would prove unremunerative, by reason of the dip of the vein and the intercalary strata and lenses of -quartz, and a more satisfactory method of working the deposit was sought. It is well understood, that, in the preparation of all clays for market, especially residuary kaolin, the most important as well as the most difficult step is the washing of the crude product. The difficulties increase with the percentage of foreign matter, especially quartz and mica, contained in the product, hence a sys-

May 1, 1906

By M. H. Harrington

The Transaclions of the Institute afford abundant evidence of the general recognition by mining engineers of the importance of a safety-lamp which will not only give warning of the presence of fire-damp, but will also indicate the proportion in which it is present.' Mining-men are only too familiar with the frequent and sudden changes that habitually occur at the working-face of a gaseous mine. Nothing illustrates more forcibly the pregnant condition of the strata enfolding the seam and the seam itself, than the fact that a circulation of perhaps 150,000 cu. ft. of air

Jan 1, 1907

By Arnulf Muan, D. P. Masse

PHASE relations in the system CoO-SiO2 have been determined as a basis for further investigations of thermodynamic properties of olivine solid solutions involving Co2SiO4 as a component. Previous data on the system CoO-SiO2 are incomplete or uncertain. Biltz and Lemke1 determined the melting point of cobalt orthosilicate as 1345°C , but Asanti and Kohlmeyer2 have later found a considerably higher temperature, 1420°C. The latter authors also studied melting relations of one mixture on the CO side and two mixtures on the SiO2 side of the orthosilicate composition and sketched a tentative phase diagram for a limited composition range of the system. However, no phase identification was carried out, and the authors left unanswered the question of the possible existence of a stable meta-silicate phase. Greig3 showed that a 90 wt pct SiO2-10 wt pct Co mixture at 1725°C consists of two immiscible liquid phases. The quenching technique was used in the present investigation. Mixtures of high-purity cobalt oxide ("Fisher Certified") and dehydrated silicic acid ("Baker Analyzed") were equilibrated in air atmosphere. The samples were then quenched to room temperature and the phases present were identified by microscopic and X-ray examination. The samples were kept in small envelopes made from thin (0.0004 in.) platinum foil. Thermodynamic data which have become available recently for Pt-Co alloys4 were used to check that the losses of COO from the oxide samples by alloying of cobalt with platinum in the present investigation were too small to change significantly the compositions of the oxide material during the equilibration. A vertical tube furnace with an 80 pct Pt 20 pct Rh resistance winding was used in runs up to 1510°C. Temperatures in these runs were measured with a Pt vs 90 pct Pt 10 pct Rh thermocouple calibrated against the melting point of diopside (CaMgSi2O6, 1391.5?C). The given temperatures as measured by this technique are estimated to be accurate to *5°C. Quench runs at temperatures above 1650°C were made with a modified Roberts and Morey5 strip furnace, using strip resistors composed of a 60 pct Pt-40 pct Rh alloy. Temperatures were measured with an optical pyrometer which was calibrated against the liquidus temperature of a mixture composed of 10 wt pct CaO, 90 wt pct SiO2 (1707°C). The temperatures measured with this technique have an estimated accuracy of +15°C. The results are shown graphically in Fig. 1. Only one intermediate phase, the orthosilicate Co2SiO4 with olivine-type structure, is stable in addition to the end members cobalt oxide and silica. The melting point of the orthosilicate was found to be 1415" ± 5°C. The metastilicate CoSiO3 is not stable at the temperatures of the present investigation. The two eutectic points in the system CoO-SiO2 where COO plus olivine, and olivine plus silica, coexist with liquid were found to be 72 wt pct COO and 1407°C and 63 wt pct COO and 1381°C, respectively. The melting point of cobalt oxide in air was taken as 1745?C, based on the previous data of Aukrust and Muan.6 Within limits of error (+ 5?C), identical eutectic temperatures to those determined in air were found when two representative mixtures were equilibrated at 1 atm O2 pressure and in an atmosphere of 84 vol pct CO2, 16 vol pct H2. This suggests that changes in oxidation state of cobalt in the condensed phases are not significant as far as their effect on the phase relations are concerned. This inference was substantiated by failure to detect7 any "excess oxygen" (i.e., oxygen in excess of that contained in Co2SiO4) in a sample of orthosilicate composition equilibrated in air 10°C above the liquidus temperature and subsequently quenched to room temperature. This work was carried out as part of a research program sponsored by the U.S. Atomic Energy Commission under Contract No. AT(30-1)-2781.

Jan 1, 1965

By Rollin A. Pallanch

THE Midvale mill of the United States Smelting Refining and Mining Company is situated on a flat site whose elevation is 50 ft above that of the Jordan River. Tailings are impounded in the area between the river and the flat upon which the mill and railroad switchyard are located. The water supply is pumped from the Galena canal which leads from the river at a point some ten miles to the south. The mill has a present capacity of approximately 1700 tons daily. It started out originally in 1926 as a 750 ton three-unit plant. The tonnage was gradually increased to 1200 tons by 1934, and in late 1935 a fourth unit was added. The accompanying flowsheet shows the principal equipment and how it is utilized. The ore is principally sulphide with varying degrees of oxidation, with individual lots ranging widely in both precious and base metal content. In each of the four individual units of the mill there will often be mixtures of as

Jan 1, 1948

By Michal Rehor, Vladimir Cablik, Peter Fecko, Tomas Lang

"1. Introduction The North-Bohemian Basin area is known for its largest Czech brown coal deposit. About 50% brown coal reserves have been exploited in the North-Bohemian Basin by the mining company of Severoceske doly, a.s. (North Bohemian Mines, j.s.c.) today. The opencast mining of brown coal naturally led to vast landscape damages. Therefore reclamation work has acquired great significance. The specific feature of Severoceske doly, a.s. mining is the fact that the mining has been realized in two geologically absolutely different localities. This fact demands even rather different methods of reclamations. The main problem at Doly Bilina localities is the occurrence of overburden rocks from the series of rocks of coal seams. These rocks are texturally light but large amounts of coal (cca 5 %) and sulphur (cca below 3 %) which makes the soil reaction extremely acid. If they appear on the surface of the dump, they create a phytotoxic area, reclamation of which requires special methods. Rocks from Doly Nastup Tusimice localities are more suitable to reclamation use, but texturally extremely heavy rocks with large fraction of physical clays appear there that can generate a sterile soil area. Their reclamation requirements are completely different from those on Doly Bilina phytotoxic areas. That is the reason of the application of some non – traditional restoration methods. This report briefly summarises the experience in application of fertilizable soils, power plant stabilizer, power plant ash and aerial sowing of charlock. The results are documented by the monitoring of the physical, mineralogical and pedological parameters of rocks in testing areas.2. Properties of Overburden Rocks in Opencast Mines Bilina and Libous The reclamation work methodology in the North Bohemian Basin is above all determined by the properties of overburden rocks which occur in the top horizon of the reclaimed sites. The research of the rocks reclamation properties dealt with four current mining localities in the central part of the basin. It concerned the Bilina and Libous mines. This chapter states the stratigraphic status properties of these sites with respect to reclamation availability. The total status of the area of interest is shown in the figure No. 1."

Jan 1, 2008

Development of automatic fire protection systems for large, mobile mine haulage equipment was initiated under Department of Interior's Bureau of Mines-FMC Corp. contract H0122053, "Improved Sensors and Fire Control Systems for Mining Equipment June 1972 to May 1973." After successfully designing and mock-up testing an effective economical automatic fire protection system, and after having demonstrated that the system could extinguish controlled fires on 100-ton capacity haulage trucks, USBM-FMC contract 110232059 was issued in June, 1973, to conduct further development and validation testing. This report documents technical progress and activity under the latter contract. Figure 1 shows areas of the two haulage trucks that were protected by the automatic fire protection systems tested during this program. Figures 2 and 3 are composites showing hardware and schematic diagrams of the systems tested.

Jan 1, 1974

By A. M. Hefny, F. P. Siew, P. G. Ranjith

Fracture initiation and propagation, being one of the most intensive subjects in rock mechanics; contribute significantly to the deformation of jointed rock masses. An experimental study on fractured granitic rock was carried out to determine the peak strength of specimen under triaxial loading conditions. The commonly observed failure mode for rock specimens in this study was found to be the shearing of the plane of weakness. The minimum peak strength of fractured rock is observed when the joint orientation is approximately 70° to the horizontal axis. Based on experimental test data, an empirical expression was developed to accommodate the effect of joint orientation and joint trace length in estimating the peak strength of fractured rocks. The predicted values of peak strength using the proposed equation well agree with the experimental results carried out on singly fractured specimens under triaxial loading conditions. The threshold stress values of crack initiation and propagation depend on joint geometrical parameters, their degree of interconnectivity, as well as surrounding stresses on the fracture plane.

Jan 1, 2003

By L. A. SCHOLL, J. K. CLEMENT

Among the problems investigated by the Bureau of Mines the coal- dust problem has received much attention. Several of the bureau's publications deal specifically with the subject. Bulletin 20° contains an account of preliminary experiments of the bureau to determine the explosibility of coal dusts as well as a review of pertinent literature. Bulletin 50 is a report of a laboratory study of the inflammability of coal dust. The first series of coal-dust explosion tests in the bureau's experimental mine at Bruceton, Pa., is described in Bulletin 56, and Technical Paper 56 presents notes on the prevention of dust and gas explosions in coal mines, and Technical Paper 84 discusses the causes of such explosions and describes methods and apparatus devised by engineers of the bureau for preventing and checking them. The present paper is a report of a detailed study of the bituminous dusts of Illinois mines, and is a part of the investigations conducted by the bureau in cooperation with the Illinois State Geological Survey and the department of mining engineering of the University of Illinois./ It is well known that bituminous coals like those found in Illinois yield dusts that may give rise to explosions of great violence. In order that proper methods might be devised for preventing dust explosions in Illinois mines it was considered desirable to obtain accu- rate information on the quantity and character of these dusts. Ex- periments and tests of dust explosions in an experimental mine as well as in a large steel gallery comparable in area of cross section to mine entries have been made by the Bureau of Mines. Similar experi- ments have been made in Austria, England, France, and Germany. Experiments under conditions similar to those of actual mining prac- tice are obviously more conclusive than tests made in a laboratory. On account, however, of the expense, time, and quantity of dust re- quired, it is not practicable to conduct large-scale tests in studying a large number of dusts and recourse must be had to laboratory apparatus and methods. Laboratory,devices for the study of coal-dust explosions have been devised by a number of investigators. Most of these were intended for qualitative tests only. Quantitative methods have been devised by investigators of the English and French mining-experiment stations." In the experiments described in this report, laboratory tests of inflam- mability were made with an apparatus devised by Dr. J. C. W. Frazer, formerly a chemist of the Bureau of Mines. Laboratory tests of inflammability have been made on more than 500 samples of dust from 100 representative Illinois mines. As a result of these tests it may be stated that: 1. The coals of Illinois when ground fine enough yield highly inflam- mable dusts which when suspended in air may give rise to violent explosions. 2. In the majority of the mines of the State the dusts adhering to the ribs are inflammable. In about one-fourth of the mines the quantity of rib dusts present in the entries is sufficient to form an explosive mixture with air. 3. Most of the road dusts are inflammable when ground to a suffi- cient degree of fineness.

Jan 1, 1916

The C.S.I.R.O. acid alumina process employs the essential steps of digestion, hydrolysis and calcination to produce pure alumina from ores too high in silica or too low in grade for the Bayer process. The two latter stages have been described in some detail previously but the digestion stage requires separate discussion since ores vary widely in composition and reactivity. Kaolinitic clays require roasting to 800°C to render the alumina soluble in the 11 per cent sulphuric acid used in the process while some ferruginous laterites require roasting to reduce the reactivity of iron minerals.The iron content of pregnant solutions is kept at a low figure by digesting at temperatures where the solubilities of ferric oxide or basic ferric sulphates are small. A two-stage, counter-current digestion is necessary to extract a high percentage of alumina from the ores and to produce a basic pregnant liquor with an SO3 : AI 203 ratio of 1'\1 suitable for high temperature hydrolysis. The second stage of digestion, called the modification stage, treats slightly acid liquors with excess of ore in the temperature range 1200-1400C.The first stage operates at 170°-1900C to extract further alumina from modification residues, using recycled acid obtained from later steps of the process. Both temperature ranges are critical for economic operation and for proper control of the iron content of solutions. In batch experiments, 30 min is regarded as a suitable retention time for digestion and modification; ores which require much longer than this are less suitable for the process. Impurities such as silica, and titanium and vanadium oxides are discarded in the residue along with iron oxide, and do not contaminate the final product. Bivalent metallic sulphates such as MgSO4, can build up in the circuit to a very considerable degree without affecting product purity.Comparison with other processes shows that the C.S.I.R.O. process is superior for control of contamination by iron, which is the major problem in acid processes. The pure intermediate product (3Al203.4S03.9H20) is also more convenient for calcination to alumina than the hydrated aluminium sulphate usually recovered in other processes. Detailed cost comparisons must await pilot-plant evaluation of the C.S.LR.O process.

Jan 1, 1964

By J. S. Lee

Alkyl hydroxamates are well known collectors for oxide copper minerals as evidenced by the large amount of published literature. Our studies on a wide variety of copper ores from around the world have shown that alkyl hydroxamates will recover most of the "floatable" oxide copper minerals from an ore. They are available commercially, and they offer many advantages over alternative technologies for oxide copper recovery. In spite of this, the full potential of hydroxamates has not been exploited in the industry. The objective of this paper is to provide relevant practical aspects and guidelines to facilitate successful application of hydroxamates in operating plants. A critical analysis of the available information and data, based on several case studies, notation testing, and microscopic analysis indicates that alkyl hydroxamates can effectively recover well-defined oxide minerals of copper, but not copper occurrences such as Cu-bearing goethite (often misidentified as cuprite) which report as Acid Soluble copper in chemical assays. Prior to any notation testing with hydroxamates, it is necessary to assess the various modes of occurrence of Acid Soluble copper using microscopic and microprobe analysis.

Jan 1, 1998

By Mario E. Rossi

Geostatistical conditional simulations are becoming increasingly popular as tools that provide models of uncertainty at different stages of a mining project. They have been used as grade control tools in daily operations, to assess the uncertainty of minable reserves at the project?s feasibility stage, and to assess mineralization potential in certain settings. Other applications include assessment of recoverable reserves, resource and reserve classification, and drill hole spacing optimization studies. All large-scale applications of conditional simulations intend to benefit from the ?correct? (or ?accurate?) characterization of uncertainty, adequately describing the variability observed from the data and its impact on the final objective. The objective of this paper is to compare the ad-hoc ?uncertainty model? provided by a traditional classification scheme with the probability intervals resulting from a conditional simulation model. It is argued that the uncertainty model derived from the use of classification schemes is of little practical use to the mining company or operation. The paper emphasizes differences in uncertainty based on the size of the mining unit considered and the extraction method, and local geological differences. Most importantly, it discusses confidence intervals for these mining units, as compared to the relative precision envisioned by a typical classification scheme. The application described in this paper is taken from a medium-sized Cu open and underground mine in northern Chile, and it demonstrates the impact of several variables on the resulting conditional simulation models. It also compares a more ?traditional? resource classification scheme applied, and the wide difference in local confidence intervals for each mining unit.

May 1, 2001

By E. W. Davis

If the tonnage of merchantable iron ore remaining in the Lake Superior district is divided by the average of the annual shipments for the past 20 years, it will be found that this ore supply will be exhausted in approximately 35 years. This computed exhaustion period would be an indication of the future activities of the iron-mining industry if it were not for the fact that merchantable ore is being manufactured from low-grade ore, of which there is an almost inexhaustible supply in the Lake Superior district. It is true that at present only the simplest of these low-grade ores are being concentrated to any considerable extent, but progress is being made with the treatment of the more complex ores, and now, in addition to 20 washing plants on the Mesabi Range, three plants are equipped with jigs for the treatment of ore that cannot be concentrated simply by washing. The latest addition to the ore-treating plants of the Mesabi Range is a magnetic roasting and concentration plant at Cooley, Minn., in which ore that cannot be concentrated either by washing or by jigging is roasted to the magnetic state and concentrated on magnetic separators. This plant is beginning its third season of operation, and while it is too soon to make definite predictions, there are strong indications that this new process may make commercially possible the manufacture of high-grade, merchantable iron ore from large quantities of low-grade ore now considered worthless. After the iron oxide contained in an ore has been converted to magnetite, almost any desired grade of concentrate can be produced, using magnetic-concentration equipment of the types now in general use for the concentration of the natural magnetites of New York, New Jersey and Pennsylvania. The conversion of hematite (Fe203) to magnetite (Fe3O4) is easily accomplished by heating the ore to a dull red temperature in a reducing atmosphere. The reaction is slightly endothermic, and while it requires 200 B.t.u. to heat to 900' F. one pound of hematite ore containing 45 per cent Fe, it requires only 100 B.t.u. to convert the oxide into magnetite. In the laboratory, using small quantities of ore, this conversion is very simple, but large furnaces suitable for commercial

Jan 1, 1939

By E. W. Davis

If the tonnage of merchantable iron ore remaining in the Lake Superior district is divided by the average of the annual shipments for the past 20 years, it will be found that this ore supply will be exhausted in approximately 35 years. This computed exhaustion period would be an indication of the future activities of the iron-mining industry if it were not for the fact that merchantable ore is being manufactured from low-grade ore, of which there is an almost inexhaustible supply in the Lake Superior district. It is true that at present only the simplest of these low-grade ores are being concentrated to any considerable extent, but progress is being made with the treatment of the more complex ores, and now, in addition to 20 washing plants on the Mesabi Range, three plants are equipped with jigs for the treatment of ore that cannot be concentrated simply by washing. The latest addition to the ore-treating plants of the Mesabi Range is a magnetic roasting and concentration plant at Cooley, Minn., in which ore that cannot be concentrated either by washing or by jigging is roasted to the magnetic state and concentrated on magnetic separators. This plant is beginning its third season of operation, and while it is too soon to make definite predictions, there are strong indications that this new process may make commercially possible the manufacture of high-grade, merchantable iron ore from large quantities of low-grade ore now considered worthless. After the iron oxide contained in an ore has been converted to magnetite, almost any desired grade of concentrate can be produced, using magnetic-concentration equipment of the types now in general use for the concentration of the natural magnetites of New York, New Jersey and Pennsylvania. The conversion of hematite (Fe203) to magnetite (Fe3O4) is easily accomplished by heating the ore to a dull red temperature in a reducing atmosphere. The reaction is slightly endothermic, and while it requires 200 B.t.u. to heat to 900' F. one pound of hematite ore containing 45 per cent Fe, it requires only 100 B.t.u. to convert the oxide into magnetite. In the laboratory, using small quantities of ore, this conversion is very simple, but large furnaces suitable for commercial

Jan 1, 1939

Teleseismic travel time residuals measured on 600-1000 km seismic arrays across the Rio Grande and East African rifts provide evidence for upper mantle low velocity zones beneath each rift of velocity contrast 6%-8%. Refraction studies show thinning of the crust below the rift axes. Regional uplift which extends hundreds of km either side of the axes, is isostatically compensated by negative density contrast at depth. Since the refraction argues against compensation by thickened crust, compensation in the upper mantle low velocity zones is suggested. Temperature effects alone can not explain the reduced velocities. Generation of a few percent of partial melt is the most probable source of the reduction. A passive extensional mechanism is investigated for the Rio Grande rift in which hot asthenosphere intrudes the lithosphere raising its temperature and generating moderate melting. It requires less than 1% extension to explain the melting but a prodigious 26% to raise the temperature from a pre-rifting continental geotherm to the solidus. Geological estimates find that extension is less than 10% over the uplift zone. Such a mechanism is possible only if the prerifting lower lithosphere geotherm lies closer to the solidus than that of stable continent. This is supported by the observed high heat flow in the Rio Grande rift uplift region which, given the long time constant for thermal diffusion, reflects elevated temperatures at depth well in advance of the onset of rifting.

Jan 1, 1987

By Juan Ayza

En este último artículo se describe el sistema de IMPINGER - como parte del muestreo y así determinar la cantidad de polvo adherido. Dicho sistema produce una presión negativa sobre el agua de un tubo, y es donde la presión atmosférica introduce el aire por un tubo central, cuya boquija está debajo del agua y a 5 mm. del fondo. En ese sentido, la mayor cantidad polvo queda en suspensión. De otro lado, se describe el método cualitativo cinematográfico donde se percibe la cantidad de polvo a través de la captación de luz fotográfica, aunque el problema es el avaluúo preciso de la sílice li-bre en el rango de polvo respirable.

Mar 1, 1956

By A. R. Hendrickson, C. F. Smith

Hydrofluoric-hydrochloric acid mixtures have been successfully used to stimulate sandstone reservoirs for a number of years. Hydrofluoric acid (HF) has a specific reactivity with silica which makes it more effective than HCl for use in sandstone. Kinetics of the reactions of HF have been studied to determine the related effects of reservoir composition, temperature, acid concentration and pressure on the spending rate of HF. Secondary effects from by-product formation are noted and described. Predictions are made concerning the improvement in productivity resulting from HF treatment of skin damage. The kinetic order of HF reaction in sandstone was experimentally determined to be first order, i.e., the reaction rate is proportional to concentration. HF reacts faster on calcite than on clay, which, in turn, is faster than the reaction rate of HF on sand. Static conditions retard the HF reaction rate. As HF is forced into cores, there is a temporary reduction as a function of flow rate and acid concentration. Extensive deposition of calcium fluoride in acidized cores was not observed. Although some CaF, was defected, it was not considered a major source of damage in cores containing moderate amounts of carbonate. Other fluosilicates could be potentially more dangerous than CaF, in reducing permeabiliry. INTRODUCTION Hydrofluoric acid has been widely used in stimulation treatments since 1935, when mud acid was introduced to the petroleum industry. Originally, this hydrochloric-hydrofluoric acid mixture was intended to remove mud filter cake, but it has since been successfully applied to many other oilfield problems. Mud acid treatments have been unusually successful in sandstone reservoirs where hydrochloric acid is unreactive due to a lack of enough calcite in the formation. The relatively small amount of hydrofluoric acid present (2.1 per cent) reacts with sand grains, clays and traces of calcite which are generally present in sandstone reservoirs. Since hydrofluoric acid (HF) is the key to mud acid success, this research effort has been dedicated to gaining a more thorough understanding of the basic chemical and physical principles involved as HF reacts. Hydrofluoric acid's reactivity with silica makes it unique in application. Other mineral acids such as hydrochloric, sulfuric or nitric are unreactive with most silicious materials which comprise sandstone formations. A typical sandstone reservoir may contain 50 to 85 per cent silicon dioxide, more commonly called sand or quartz. Hydrofluoric acid reacts as follows: 4HF + SiO2 + SiFO + 2H2O The silicon tetrafluoride (SiF,) is a soluble gas, in some ways similar to CO2, and is capable of undergoing further reaction when held in solution by pressure. These reactions will be considered in detail later. Kinetics of the reactions of HF have been studied to determine the effect of reservoir composition, temperature and pressure on the spending of the acid. Secondary effects from by-product formation have been noted and described. The individual reactions of HF on quartz, glass and clay are reported. Mathematical correlations have been drawn, then applied to studies of HF spending in cores obtained from actual producing sandstone formations. The research reported herein is only the beginning of a continuing approach to better understanding and use of HF in petroleum reservoirs. THEORY AND DEFINITIONS Through the years, a concentrated effort has been made to understand the effects of many variables on hydrochloric acid (HCI) spending in limestone. Hendrickson el al., have given mathematical relationships for HC1 reactions which made possible the engineered approach to acidizing. The same variables—temperature, acid concentration, formation composition, pressure and permeability-porosity relationships—which affect HC1 behavior in limestone also govern HF behavior in sandstone. Insoluble by-products of HF reaction have been isolated and identified. Their effect on fluid flow has been measured under varying conditions in an attempt to evaluate the extent of possible damage and means of eliminating it. In general, HF follows the same reaction paths as HCI. It will react with limestone and dolomite with speed and ease. Thin sections of acidized cores show the reaction of HF with limestone or calcite faster than its reaction with either clay or sand. When HF reacts with calcite (CaCO,), theoretically, calcium fluoride (CaF2) is precipitated, and has been blamed as a major cause of reduced permeability. On the other hand, pH and pressure such as that encountered in an underground formation under acid treatment definitely retard CaF2 formation,' so the whole question of CaF, deposition in wells is a subject for study.

Jan 1, 1966