Search Documents

By Rudolf E. Greuer

This study concerns itself with two topics of the mine ventilation - mine fire interface which, when the work for this study began, did not seem to receive sufficient attention. Section 1: Comments on Spontaneous Combustion of Coal in Mines It is attempted to describe heat generation, heat and oxygen transport, in such a way that existing experimental data for U.S. coals can be used to assess conditions inducive to spontaneous heatings quantitatively. Investigated are, in particular, critical air velocities, minimum sizes of coal accumulations, moisture contents and the influence of mining factors. An extensive, practice oriented literature survey is included. Section 2: The Early Detection of Mine Fires by Assessment. of Mine Gases The suitability of the major constituents of combustion products for an early detection of fires is discussed. The same is done for gas concentration ratios. Since it was felt (at least at the time when this report section was written) that the value of the carbon monoxide/oxygen deficiency ratio was overestimated, the usefulness of monitoring this ratio as compared to monitoring CO concentrations was critically investigated. The state of art concerning instrumentation and organization of fire detection systems is reviewed also.

Jan 1, 2011

By William Campbell

(Cleveland Meeting, October, 1912.) [SECRETARY'S NOTE.-To avoid repetitions of foot-notes, references to authorities are made in the paper by means of figures, referring to a numbered list in the appendix.-J. S.] I. INTRODUCTION. IN the olden days the making of alloys was au art, and the secrets of the craft were jealously guarded. To-day it has become a science, though the old ideas in regard to the secrets and formula are dying hard. Modern progress may be attributed to scientific research and testing of materials, and the substitution of chemical analytical control for " cook-book " methods. We know to-day a great deal about the constitution of alloys, the reasons of the change in structure and physical properties by heat and mechanical treatment; and this new knowledge is due for the most part to the physical chemist and metallographist, who have shown us that alloys are simply solutions, and as such obey definite laws. The application of the theories of solutions and of the phase rule tells us what ought to happen when our alloys are in a state of equilibrium. The working-out of the temperature-composition diagram (thermal diagram) for numerous alloys has thrown a light on the structure and constitution which has dispelled most of the darkness in which we labored before the advent of metallography. The work began with the determination of the freezing-point curves, and here the research of Le Chatelier,1 Gautier,2 Roberts-Austen,3 and the other pioneers broke the ground. Next the physical chemists, Tammann,4 Rooseboom,5 Bancroft,6 and their colleagues, showed us the complete thermal diagram and its meaning. Then the researches of Heycock and Neville 7 on the Cu-Sn series and of Shepherd 8 on the * Associate Professor of Metallurgy, Columbia University in the City of New York.

Dec 1, 1912

n the early days of the Hauraki goldfield (1866 to 1889) almost the only system of ore treatment was wet crushing followed by copper plate amalgamation. A further saving of bullion was in most cases obtained from the tailings by means of pans or berdans. Though this system was not always as efficient as might have been desired it answered fairly well for the bulk of the gold-bearing quartz of the Thames and Coromandel districts, where the gold occurs chiefly in the form of visible particles, and there is not a great deal of silver. It failed, however, with most of the ore found in the Upper Thames or Ohinemuri district, especially in the Karangahake and Waihi portions of the field. In those days the cyanide process was not, and the usual prescription of the mining " expert" was smelting. At Karangahake, many attempts were made to discover a payable method of treatment for the so-called" refractory" ore, but on thewhole with very 'little success, and the district struggled along for a number of years without adding very materially to the production of gold in New Zealand. At Waihi, the Martha Co.'s stamp battery treated by wet crushing and copper plate amalgamation some 18,000 tons from the Martha Reef, worth probablyat least £4 per ton, but the average return was considerably less than £1 per ton, a sum which barely paid working, expenses, and consequently the shareholders were glad...

Jan 1, 1903

By R. Boom, L. Holappa

In the present paper, microstructure changes of solid-state reduction of industrial chromite pellets and lumpy ore were investigated with SEM/EPMA. To simulate the reactions in the packed bed zone of the Submerged Arc Furnace (SAF), carbon monoxide was used as the reducing agent, with the presence of graphite in proximity to chromite. The experiments were carried out at 1500 °C. Scanning electron microscopy was used to observe and analyse the structure and composition changes of the chromite samples. It was found that reduction of lumpy ore generally took place slower than that of pellet. In all samples, chromite reduction proceeded faster in the outer part of the sample than in the centre part. The reaction mechanism is discussed on the basis of experimental results and earlier investigations. The possibilities to optimize the FeCr production process are also discussed.

Jan 1, 2007

By B. J. Moore

This publication contains analyses and related source data for 675 natural gas samples from wells and pipelines in 24 States and 5 foreign countries. The samples obtained and analyzed during calendar year 1980 are included in tables 1-4. Those samples included in tables 5-7 were collected during the years 1960 through 1979. However, permission to publish the analyses of those samples was not given until the past year when the operators were again contacted to seek release of the information. All of these samples were collected as a part of Bureau of Mines investigations of the occurrences of helium in natural gases of countries with free market economies. This survey has been conducted in the United States by the Bureau of Mines since 1917. In late 1965, the survey was expanded to include foreign gasfields. The analyses published herein were made by mass spectrometer and a special helium analysis apparatus, which are described in Bureau of Mines Bulletins 4862 and 576. The results of the investigation of the occurrences of helium are published annually to make the information available as soon as possible to the gas industry and the general public. Twenty-two previous publications have presented the results of 12,152 gas analyses made prior to 1980. The first three, Bulletins 486,' 576,5 and 617,6 contain analyses and related source data on 5,218 gas samples collected from 1917 through 1980. The other

Jan 1, 1981

By Timo Niitti, Antti Rinne, Janne Turunen, Sami Grönstrand

"This paper describes novel methods to enhance the flow dynamics of a mechanical flotation cell that can be applied to an existing installation. There are several reasons to alter the flow dynamics. The most common motivation is to improve the metallurgical performance of the cell, for instance, to improve the flotation recovery in particle size ranges that are normally difficult to recover.The flow dynamics enhancements are associated with the geometry of the rotor-stator area and additional features in the tank. The rotor-stator area has been modified to provide more concentrated turbulent kinetic energy or respectively more pumping efficiency with less attrition to the slurry. The tank can be fitted with various geometrical features, aimed to create a desired particle suspension profile. Depending on the targeted particle size range and application, badly selected or designed features can also have a negative effect on the metallurgical results.Besides new flotation equipment, the enhancements can be applied to existing flotation cell installations, thus enabling improvements in the mixing profiles, solids suspension, tank sanding and metallurgical performance of operating flotation circuits. Results of several tests carried out in existing plant operations are presented, concerning both flow variables and metallurgy.The common factor to above-mentioned enhancements is the use of modern computational fluid dynamics tools in the design phase, as well as the validation of the obtained CFD results in laboratory and production scale. Validated variables include mixing profile, power draw and local air hold-up.The paper demonstrates the effects of various flow geometries on the mixing profiles and metallurgical results of existing mechanical flotation cells. It shows how modern computational fluid dynamics analysis can be used to screen and select different approaches before carrying out costly trial-and-error experiments in plant scale."

Jan 1, 2006

By Robert Stefanko

With passage of the Clean Streams Act of the Commonwealth of Pennsylvania and its impact on the coal industry, considerable research has been conducted to explore various approaches to the problem, including deep-well disposal. Available drillhole data from gas and oil wells were used to develop cross -sectional maps for various portions of the state and potential disposal zones were evaluated. Bethlehem Mines Corp., faced with a severe water problem at its Marianna operation in Washington County, cooperated with the Dept. of Mining at The Pennsylvania State University in establishing a 1500-ft well into the Salt Sands for the purpose of determining the feasibility of mine water disposal. The thickness, porosity, and permeability of the formation at the well site proved to be below what had been anticipated from drillhole data. Further, subsequent hydraulic fracturing did not improve the flow characteristics of the well; pumping pressures remained in the range of 1800-2000 psig for disposing of water at the rate of 150 gpm. The legal problems of disposal at the site were very formidable. When the Salt Sands proved to be less than satisfactory, permission could not be obtained to dispose in other promising formations. The paper details many of the problems associated with the experimental well and makes an assessment of the potential for deep-well disposal of mine water. The concept of disposing of liquid industrial wastes by deep-well injection is not a new one. Brines associated with crude oil long have been disposed of in this manner, with the additional benefit of aiding secondary oil recovery. More recently, with the expansion of nuclear energy, the lethal, highly radioactive wastes which are by-products of the fission process have created severe disposal problems. During the past ten years, a variety of industries have resorted to subsurface disposal, some of the details of which are given e1sewhere.l,2 The list reveals wide variations in injection rate, pumping pressure, cost, and waste disposition. Included are successful installations in Western Pennsylvania. Enactment of more restrictive clean-water legislation in Pennsylvania recently had a great impact on the coal industry. Among its provisions was the reclassifica-tion of most mine water as industrial waste whose dis-posal is prohibited in any stream of the Commonwealth. This had the effect of accelerating research in a variety of areas, although treatment methods still retained primary interest. When a feasibility study of deep-well disposal was proposed to the Pennsylvania Dept. of Mines and Mineral Industries, the Coal Research Board (CRB) approved it. This paper summarizes the efforts on this project. Acid mine water is a chemically complex liquid. having no definite quantitative relationship among its constituents. However, it is the iron disulfide (FeS2) associated with practically all coal seams that produces the objectionable products present in acid mine water when combined with air and water. The principal contaminants are sulfuric acid (H2SO,) and ferric hydroxide (Fe(OH)2. Ferric hydroxide is a rust-colored gelatinous precipitate that coats stream bottoms and destroys aquatic life. However, other ions and bacteria are present in acid mine water in varying amounts.

Jan 1, 1971

By John W. Moore

The discovery of porphyries in petroleum by Treibs (17-19) is one of the most significant achievements relating to the origin of petroleum. The presence of these remnants of chlorophyll and hematin in petroleum has immediate practical interest in several aspects of the petroleum industry. Because of their interfacial activities and film-forming tendencies, the metal-porphyrin complexes may be expected to affect the wettability of petroleum-reservoir rock surfaces and influence the flow of fluids in these reservoirs. Also, studies of the relationship of trace elements and porphyrins in petroleum may be expected to yield valuable information on source beds and petroleum migration. Finally, the extreme stability of several metal-porphyrin complexes complicates removal of these metals from some petroleum stocks where they exert deleterious effects on processing and utilization. Metal-porphyrin complexes are commonly associated with the asphaltic residues of crude oils in which they occur (8, 9, 15). However, investigations in this and another laboratory (15) show that small amounts of these complexes often remain in partly refined petroleum products, such as thermally cracked distillates and deasphalted stocks.

Jan 1, 1957

By James Anstey

BHP Billiton?s Cannington facility is a mining and minerals processing plant near Mt. Isa in Central Queensland, Australia, producing silver, lead and zinc. Mine ore is processed in a concentrator, which consists of grinding, flotation, thickening and filtration. Grinding is carried out in a fully autogenous (AG) mill. The mill operates in closed circuit with a pebble crusher. Throughput is approximately 380 tph. Cyclone overflow from the grinding circuit is fed into a flotation circuit for the recovery of lead, zinc and silver. Two concentrates are produced (lead and zinc), which are then thickened and filtered. The filtered concentrate is transported by road to a rail receiving station. From here the concentrate is railed to port in Townsville for shipment to the smelter. Matrikon and Engineers at BHP Billiton?s Cannington Mine have used ProcessACT to develop a flexible, nonlinear dynamic simulator for the grinding circuit to further enhance process understanding, as well to investigate various optimization strategies. An online charge volume estimator was also developed for the AG mill to aid in the understanding of overload conditions, which for the previous two months had been the primary contributor to downtime. The models were developed using a combination of first-principles modeling along with input-output dynamic responses. Examples of models used include: Morrell ?C? model for power and charge shoulder/toe angle prediction; Whiten?s mixing model for breakage and hold-up; Nageswararao cyclone model for predicting cut size; slurry recovery and water recovery. The composite model simulates system dynamics starting from the stockpile reclaim system and finishing at the feed for the flotation process. The objective was to provide a tool that assisted Cannington in understanding their Grinding Circuit and allowed them to develop and evaluate circuit optimization strategies. BHP Billiton Cannington Mine is now considering development of a Grinding Circuit Optimizer utilizing the models developed for the simulator.

Apr 1, 2005

By Jean Cayouette, Paul Blatter, Paul Cousin

"The Laronde mill was commissioned in 1988 and has been treating the Laronde Penna ore since 2000. The Laronde plant, situated in the Abitibi region of Quebec, has experienced mill expansions to accommodate 7500 mtpd and to recover gold and silver as well as important amounts of base metals (Cu, Zn, Pb). Ten sequential metallurgical and environmental processes are responsible for metals recovery and process viability. Over 200,000 ounces of gold, 4,5 million ounces of silver, 7000 tonnes of copper, and 78,000 tonnes of zinc are produced annually.In 2008, the Goldex plant began trucking high grade (35-45 g/t Au) pyrite sulphide concentrate (TCGO) for gold extraction at a newly constructed treatment plant, increasing gold output at Laronde by 40,000 ounces. In 2009, the high gold grade Lapa ore processing facilities were annexed to the Laronde plant increasing output by 120,000 ounces of gold. TCGO and Lapa productions are forecasted until 2018 and 2015 respectively, with known reserves of each mine.Today, up to 140 permanent employees run and optimise the Laronde plant operation. As a result, Laronde has intricacies intrinsic to a large and varied operation. The paper will outline the metallurgical highlights, challenges, and future outlook related to the treatment of each ore type (Laronde, TCGO, and Lapa).INTRODUCTIONFollowing the 2000 to 2003 expansions, the Laronde plant evolved into a mature milling complex with developed processing, man power, and water treatment capabilities able to accommodate the complex Laronde ore. The ore requires a series of grinding, copper/lead flotation and separation, zinc flotation, zinc tails precious metals leaching, followed by a counter-current decantation circuit and Merrill Crowe precipitation. A paste backfill and SO2-air cyanide destruction operate intermittently. The tailings area has a dedicated cyanide destruction and metals precipitation plant prior to water recycling to the mill. A biological water treatment plant was put into service in 2004 to address the build-up of thiocyanate in the tailings ponds at Laronde. This was the result of the high sulphide content of the Laronde ore and 90% recirculation of the process water. The plant uses bacteria to oxidize and destroy thiocyanate, and removes phosphate from the water before it is released to the environment."

Jan 1, 2011

By D. N. Bigby

This paper concentrates on ground control innovation in Europe since the first Morgantown conference, mainly from a UK perspective. In particular, it describes the rock engineering and ground control tools developed to address the mine support and design problems associated with coal mining at great depth in areas influenced by previous workings. The differences in approach across the Western European industries are also examined. Perhaps the most significant change in the period has been in the science of coal mine rock mechanics itself, with support design now based firmly on measurement, analysis and understanding. The ground control innovations described here have played their part in increasing the efficiency with which coal is mined and in increasing safety to the extent that fall of ground accidents are now rare.

Jan 1, 2006

By C. R. Larsen, R. G. Bradburn, A. L. Mular, B. C. Flintoff

"Following the acquisition of grinding- circuit data at Brenda Mines Limited for simulation purposes, various methods to mass balance the circuit were evaluated. Unfortunately, different answers were obtained for different balancing methods. A data-adjustment procedure was therefore developed. The procedure assumes that all ""best-fit"" criterion. A search is conducted with the minimum set of water masses and narrow size ranges of solids around the circuit (called search variables), which permit the computation of any of the measured data points. Search variables are used to calculate measured values for an objective function of the form: [ ] where W, is a weighting factor•, M1 is a measured value and M. is a corresponding . value calculated from search vanables. The best values of M, are those which minimize R. The above method is compared with others that have been utilized for mass balancing circuits."

Jan 1, 1976

By J. Cooperman

THE INVESTIGATION was carried out in three stages, depending on the objectives of the work and the kind of equipment used. The first stage involved testing of 11 representative Alabama coals, the source of which is given in table 1. The objective was to find whether these coals could be gasified raw by the Lurgi method, and the equipment used was a 4-inch batch generator (to be described later). This generator proved too small and difficult to control to provide adequate amounts of products under continuous operating conditions for testing. For the second stage, a 6-inch batch generator was used, which was provided with facilities for superheating the steam-oxygen mixture and for synthesizing additional methane from the residual carbon monoxide and hydrogen in the primary Lurgi gas. Selected Alabama coals, Pittsburgh-bed coal from West Virginia, "Disco," and anthracite were used. For the third stage of the work, a continuous generator of 1 square foot grate area, following closely the design of the industrial generators operated in Germany, was provided. This generator was designed by 0. Hubmann, engineer for the Lurgi company, and was expected to give results closely simulating industrial-scale apparatus. The purpose of this equipment was to test prepared materials shown to operate smoothly in the 6-inch generator under conditions approximating as nearly as possible those prevailing in industrial practice. Work of the first stage showed that Alabama coals could not be used in the Lurgi process without first destroying the coking power.

Jan 1, 1951

By D. J. Parker, D. Harrington, L. H. Harrison

"INTRODUCTION The necessity for protection against the hazards of lightning manifests itself from time to time in the mining industry by reason of loss of life, damage to electrical equipment, fires in surface structures at mines, and accidents in the handling and use of explosives. This paper is intended to assemble, correlate, and present some of the salient points embodied in the available literature on the subject and at the same time give some factual data concerning instances of such loss of life and damage to property, with special application to the mining industry.The annual loss of life and destruction of property by lightning is considerable; the former may be prevented to a limited extent, though use of common sense as to exposure is required and not always followed; the latter can be prevented to a considerable degree. The manufacturers of electrical equipment, through improved types of lightning arresters, have done much toward the protection of electrical equipment, with consequent safeguarding of life and of property. Education based on unfortunate experiences has gone far to discourage the handling of explosives and blasting accessories during thunder storms, especially in open pits and quarries, and to a much smaller extent in underground workings. The lowly lightning rod plays an important role in the protection of certain types of buildings (especially isolated buildings), stacks, monuments, and other structures.LIGHTNING PHENOMENAIn 1751, Franklin proved that, lightning was simply a visible display of electricity - an extended spark; and until a generation ago little had been added to his exposition to define the various phases of the phenomenon. Matters pertaining to lightning are discussed in the following references:"

Apr 1, 1948

By S. Nikolic, O. O. Kehinde-Philllps, O. T. Djamgouz, D. H. Rousell

"A bulk mining method is employed at the Lockerby mine resulting in the formation of large muck-piles. If these muckpiles remain in the stopes for some time they may agglomerate to the extent that the muck cannot be removed by a scooptram. A laboratory investigation was undertaken with sulphide material from the mine in order to detemine the time that oxidation begins and the flowability of the material as a f unction of several factors. The laboratory results are applied to the conditions in the muck-piles.The time of the beginning of oxidation of the material decreases as the sulphide composition, water content and availability of air increases. Oxidation is retarded by the addition of a copper sulphate solution instead of water. The unconfined yield force (strength} of the material increases with an increase in the sulphide composition, water content and time. The material ceases to be free-flowing before there is visible evidence of oxidation and this suggests that oxidation actually begins earlier and that agglomeration is also due to the capillary action of water.Broken ore should be removed from the stope prior to the time a muck-pile ceases to be free -flowing-perhaps as early as two days f or high-grade ore and 5 days f or low-grade ore. In order to control dust, 1.4 weight per cent of a 5 per cent solution of copper sulphate should be added 10 the muck-pile rather than water. This inhibits oxidation and increases the time that a muck-pile remains free-flowing."

Jan 1, 1984

By Arno C. Fieldner, Howard I. Smith, J. W. Paul, SAMUEL SANFORD.

Many mine samples of coal are analyzed each year in the laboratories of the Bureau of Mines. The analyses are made in connection with investigations relating to fuels belonging to or for the use of the United States Government, the causes of accidents in coal mines, the geologic relations of coal beds, and the character and the value of the coal and lignite in the public lands. The systematic collection and analysis of such samples in connection with fuel investigations was begun in 1904 at the Government fuel-testing plant at the Louisiana Purchase Exposition, and was under the direction of the United States Geological Survey for six years. Descriptions of the coal samples collected between the beginning of this work, July 1,1904, and the transfer of the fuel-testing and mine-accident investigations to the Bureau of Mines, July 1, 1910, were compiled and published in Bureau of Mines Bulletin 22.a Descriptions and analyses of samples collected during the fiscal years 1911 to 1913 were published in Bureau of Mines Bulletin 85.b The present bulletin presents analyses and descriptions of samples collected during the fiscal years 1913 to 1916. In order that the material in this bulletin may be used to supplement that presented in Bulletins 22 and 85, the same plan of geographical classification has been followed, the analyses and descriptions of the samples being grouped in alphabetical order according to the State, county, and town near which the mines or prospects sampled are situated.

Jan 1, 1918

By J. F. Barkley

To aid in winning the recent world war, the Bureau of Mines conducted a National Fuel Efficiency Program, directed to commercial plants throughout the Nation, to save greatly needed fuel, a basic resource vital to industrial production. In planning this program it was realized that to accomplish a satisfactory reduction in fuel consumption in any plant, it would be necessary to reach, enthuse, and usually educate to some extent the actual operators of the various types of plant equipment. A major part of the programs consisted, therefore, of visits to plants and work with the operators, including a review with them of their operating conditions and of educational and guiding literature pertinent to the operating problems involved. Through a Nation-wide organization, local volunteer engineers served in making visits to local plants. Each cooperating plant appointed an employee as the "waste chaser," who headed the work of saving fuel in that plant. The educational literature was designed to interest the operator, as well as serve as a guide in eliminating waste of fuel. Volumes have been written on many subjects relating to the saving of fuel. Writings of the treatise type contain considerable good information but do not have wide appeal and probably will be read only by a few studious operators. The problem is not one of getting clown on paper everything that the experts know and would like to have the operator know, but rather to write something that will actually interest the operator and stimulate him to action. Past experience led to the adoption, therefore, of the "quiz-sheet" type of writing, using a quiz sheet of not more than two pages for any principal item. The results obtained during the National Fuel Efficiency Program in many types of plants further demonstrated that the short quiz sheet is satisfactorily appropriate and does accomplish results. Each sheet was prepared and checked by many engineers expert in the particular subject matter of the sheet. Committees of men with much experience in the manufacture and operation of equipment and in the

Jan 1, 1947

Development and Validation of Ore Characterisation Test and its Use in Variability Campaigns of Comminution Circuits Impact testing was developed by assessing the fragmentation characteristics of ore samples after controlled impact. Standard methods are, however, limited to relatively large and coarse samples, which thus precludes their use in early stages of projects, as well as where only drill cores are available. The method described in this paper is based on the same concepts of controlled ore breakage, but using relatively smaller samples. It is particularly useful in assessing the variability of ore characteristics in early stages of greenfield projects, as well as in predicting the performance of existing grinding circuits. A validation program was carried out in which a good adherence to the original test results was obtained. The results were used for (a) simulation of a copper comminution circuit as a function of the ore characteristics, and (b) evaluation of sampling protocols used for assessing fragmentation characteristics.

Sep 13, 2010

By E. Spencer

Overexposure to hazardous noise has been found in most mining sectors, with up to 100% of the surveyed workforce experiencing a noise dose over the Mine Safety and Health Administration (MSHA) permissible exposure level (PEL). As a result, miners show elevated rates of hearing impairment of 70-90% by retirement age. To help manage noise exposures, the National Institute for Occupational Safety and Health (NIOSH) developed the Determination of Sound Exposures (DOSES) software and implementation guide for use by mine management and safety personnel. The software relies on a time-motion study that profiles the worker?s daily activities. Observations about the worker?s location and tasks or other activities are recorded along with the start and end time, to determine the duration of the tasks, so they can later be matched up with the noise data. The software gives the user the option of assessing dose relative to the MSHA PEL, the Action Level or the NIOSH Recommended Exposure Limit. The software generates a variety of interactive onscreen displays showing where, when, and how the worker?s noise dose accumulated. It also can generate customizable printed reports. These outputs can be used to highlight the tasks, locations, and times that are associated with the greatest amount of the worker?s noise exposure. DOSES simplifies the record keeping and analysis associated with time-motion studies and worker noise exposures, so mine management can make engineering noise control or administrative control decisions to limit the noise over-exposure of their workers.

Jan 1, 2010

By Russell J. Foster

Many important materials are derived entirely or partially as byproducts of primary copper, lead, and zinc production. This U.S. Bureau of Mines report examines the collective role of byproducts with regard to the economics of domestic mineral production, and their individual significance in terms of dollar value, end uses, and strategic considerations. The study also analyzes circumstances that have affected the competitiveness and structure of the U.S. copper, lead, and zinc industries, and factors that impact byproduct availability. These factors include production capacity at smelters and refineries, process technology, changing sources and composition of ores, regulations, foreign ownership, and byproduct demand and price. Policy considerations regarding stockpiling, regulations, and research are assessed.

Jan 1, 1991