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By Elliot P. Rexford

IN the early days of concrete construction, the question of quality of sand or gravel to be used as aggregate in concrete was given little or no consideration. If the construction engineer had sufficient quantity for his structure within a reasonable distance, he was contented and gave no thought to the possibility that the material might have adverse physical, chemical, or thermal properties which could cause future deterioration of his concrete and possible failure of his structure. Today a very different situation exists. With the building of larger and larger concrete structures, with a longer and longer life expectancy, the quality of the aggregate material has become of major importance. Even in small concrete structures aggregate quality cannot be passed off lightly and the quality of the aggregate must be such as to give the anticipated life without costly maintenance. The first question to arise in the selection of an aggregate is what makes a sand or gravel suitable or unsuitable for use in concrete, and how can its quality be judged. No one rock type can be depended upon to furnish sound durable material in all instances. Granitic rocks, for example, make very satisfactory aggregates in some cases, but they are among the most unsuitable of materials when they are fractured, weathered, or highly micaceous. Limestones make excellent concrete aggregates on the one hand, and on the other they may be unsound and lack durability if they contain appreciable clay, they may have a harmful chemical reaction with the cement if they contain amorphous silica, or they may have thermal characteristics which make them highly unsuitable for use in concrete. Each rock, gravel, or sand must be proved on its own merits for the particular job under consideration. The selection of suitable aggregate materials may be divided into two major phases, the geological phase which is carried on largely in the field, and the testing phase which of course is a laboratory problem; both are important. Very often the geological phase alone is sufficient for the selection of satisfactory aggregates for minor structures but for major structures both phases must be thoroughly investigated. Geological Phase In the southwest part of the country nearly every major rock type, igneous, metamorphic, and sedimentary, may be found with all imaginable intermediate phases and in all imaginable stages of alteration. Frequently very different rock types, different as to geological age, composition, and condition occur very close together. Alluvium and stream-bed sands and gravels will consist of many different rock types and even ledge rocks may vary radically as to texture and composition within the area of a quarry site. Some of the rocks make suitable aggregate materials whereas others are highly deleterious in concrete. Too often the good and the bad occur together and more than ordinary caution is required in aggregate selection. Aggregate Sources: Concrete aggregates are usually obtained from stream-bed sands and gravels or from ledge rocks. Each has certain favorable and unfavorable characteristics and it is sometimes necessary to investigate both types to determine the most suitable source for a specific structure. Stream Beds: The predominant sources of aggregate materials in southern California and Arizona are stream beds. Vast quantities of sands and gravels are brought from the mountain ranges by the rivers during times of flood but most of these streams are dry a large part of the time and hence these deposits make easily accessible sources of aggregate materials. From many standpoints stream-bed materials make very acceptable aggregates. The gravel pebbles and the sand grains are

Jan 1, 1951

By Elliot P. Rexford

IN the early days of concrete construction, the question of quality of sand or gravel to be used as aggregate in concrete was given little or no consideration. If the construction engineer had sufficient quantity for his structure within a reasonable distance, he was contented and gave no thought to the possibility that the material might have adverse physical, chemical, or thermal properties which could cause future deterioration of his concrete and possible failure of his structure. Today a very different situation exists. With the building of larger and larger concrete structures, with a longer and longer life expectancy, the quality of the aggregate material has become of major importance. Even in small concrete structures aggregate quality cannot be passed off lightly and the quality of the aggregate must be such as to give the anticipated life without costly maintenance. The first question to arise in the selection of an aggregate is what makes a sand or gravel suitable or unsuitable for use in concrete, and how can its quality be judged. No one rock type can be depended upon to furnish sound durable material in all instances. Granitic rocks, for example, make very satisfactory aggregates in some cases, but they are among the most unsuitable of materials when they are fractured, weathered, or highly micaceous. Limestones make excellent concrete aggregates on the one hand, and on the other they may be unsound and lack durability if they contain appreciable clay, they may have a harmful chemical reaction with the cement if they contain amorphous silica, or they may have thermal characteristics which make them highly unsuitable for use in concrete. Each rock, gravel, or sand must be proved on its own merits for the particular job under consideration. The selection of suitable aggregate materials may be divided into two major phases, the geological phase which is carried on largely in the field, and the testing phase which of course is a laboratory problem; both are important. Very often the geological phase alone is sufficient for the selection of satisfactory aggregates for minor structures but for major structures both phases must be thoroughly investigated. Geological Phase In the southwest part of the country nearly every major rock type, igneous, metamorphic, and sedimentary, may be found with all imaginable intermediate phases and in all imaginable stages of alteration. Frequently very different rock types, different as to geological age, composition, and condition occur very close together. Alluvium and stream-bed sands and gravels will consist of many different rock types and even ledge rocks may vary radically as to texture and composition within the area of a quarry site. Some of the rocks make suitable aggregate materials whereas others are highly deleterious in concrete. Too often the good and the bad occur together and more than ordinary caution is required in aggregate selection. Aggregate Sources: Concrete aggregates are usually obtained from stream-bed sands and gravels or from ledge rocks. Each has certain favorable and unfavorable characteristics and it is sometimes necessary to investigate both types to determine the most suitable source for a specific structure. Stream Beds: The predominant sources of aggregate materials in southern California and Arizona are stream beds. Vast quantities of sands and gravels are brought from the mountain ranges by the rivers during times of flood but most of these streams are dry a large part of the time and hence these deposits make easily accessible sources of aggregate materials. From many standpoints stream-bed materials make very acceptable aggregates. The gravel pebbles and the sand grains are

Jan 1, 1951

By Elliot P. Rexford

B. C. Burgess-—Prior to hearing this paper presented at the San Francisco meeting, I travelled by car from Yuma, Ariz., across south-central California and up through the San Joaquin Valley. After hearing the paper I returned by the coast route to San Diego then along the Mexican border to Yuma. The striking feature of these trips, related to this paper, was the dry river and creek beds at a time of year not the dry season. Contrasted with this was the wasteful use of water in irrigation canals and laterals. Poland says "at least 90 pct of the ground water pumped is used for irrigation." That being the case, it would appear that first consideration should be given to conservation of this use. Probably a small part of this is actually reaching the plants. Some measure of this loss between pump and crops would be revealing. Methods that might be employed to reduce this loss are pipe lines and spraying of some crops such as the banana planters are using in Central America. Another idea which might be investigated is to line canals and ditches with some water-repelling mineral like pyro-phyllite. Perhaps a comparatively thin sprayed-on

Jan 1, 1951

By Elliot P. Rexford

B. C. Burgess-—Prior to hearing this paper presented at the San Francisco meeting, I travelled by car from Yuma, Ariz., across south-central California and up through the San Joaquin Valley. After hearing the paper I returned by the coast route to San Diego then along the Mexican border to Yuma. The striking feature of these trips, related to this paper, was the dry river and creek beds at a time of year not the dry season. Contrasted with this was the wasteful use of water in irrigation canals and laterals. Poland says "at least 90 pct of the ground water pumped is used for irrigation." That being the case, it would appear that first consideration should be given to conservation of this use. Probably a small part of this is actually reaching the plants. Some measure of this loss between pump and crops would be revealing. Methods that might be employed to reduce this loss are pipe lines and spraying of some crops such as the banana planters are using in Central America. Another idea which might be investigated is to line canals and ditches with some water-repelling mineral like pyro-phyllite. Perhaps a comparatively thin sprayed-on

Jan 1, 1951

By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

By Paul M. Tyler

Higher freight rates and better methods of beneficiation now may make it more economical to open inferior deposits closer to a glass factory than to work higher-grade deposits farther away. Nature of impurities and special treatments as well as common practice of sulphuric acid leaching are described. HISTORICAL concepts of the economics of the glass-sand industry are changing rapidly. The greatly expanded demand for glass containers combined with higher freight rates on raw materials and manufactured products have induced a migration of glass factories toward densely populated centers and the creation of new standards of place value for substandard sand deposits. This migration has been facilitated by the construction of pipelines to bring cheaper natural gas and liquid fuel to large cities and may be further speeded by the adoption of modern mineral dressing methods to permit economical utilization of local raw materials. Our national resources of naturally high-grade silica sand are abundant, but most of the best deposits are situated so far from large centers of population that it now costs $3.00 to $5.00 a ton to carry the sand from the mine to the optimum site for a factory making beverage bottles, scientific and electrical glassware, and miscellaneous blown and pressed ware for local markets. It follows that on the basis of freight savings alone it may be economical to use material from inferior deposits closer to the factory even though the f.O.b. cost of mining and treatment may be much higher than at a higher grade deposit farther away. Particle-size distribution is a feature of glass-sand specifications. As long as glassmakers insisted upon having their sand principally coarser than 100-mesh, any material was automatically excluded from consideration that could not be purified without fine grinding or other drastic treatment which greatly reduces the size of the quartz grains. However, re- cent large-scale tests in Norway' showed that finely-crushed quartz used in a soda-lime-silica glass batch caused it to melt and become refined appreciably faster than when ordinary coarse (Belgian) sand was employed. Dust losses were negligible. Since the pre-war cost of sand was only 3 pct of the manufacturing cost of the glass, it was deemed economical to pay twice as much for crushed quartz because of the saving in wear and tear on the furnace walls. In the author's unverified opinion, sand ranging in size between 150 and 400-mesh would probably be superior to that in the more usual range of 20 to 100-mesh. Former objections to fine sand (other than dust) were doubtless fostered by the natural concentration of impurities in the finer sizes. Ordinarily the most objectionable, as well as the commonest, impurity from the standpoint of the manufacturer of any but the cheaper qualities of colored glass is iron. No natural sands are really pure silica. Even water-clear quartz crystals are likely to contain impurities in the form of solid solution as well as inclusions which cannot be eliminated except by chemical treatment that will break down the silica lattice. Pure white pegmatite quartz will usually analyze 0.01 pct or more of iron oxide, and ordinary vein quartz and the quartz grains in most

Jan 1, 1951

By Paul M. Tyler

Higher freight rates and better methods of beneficiation now may make it more economical to open inferior deposits closer to a glass factory than to work higher-grade deposits farther away. Nature of impurities and special treatments as well as common practice of sulphuric acid leaching are described. HISTORICAL concepts of the economics of the glass-sand industry are changing rapidly. The greatly expanded demand for glass containers combined with higher freight rates on raw materials and manufactured products have induced a migration of glass factories toward densely populated centers and the creation of new standards of place value for substandard sand deposits. This migration has been facilitated by the construction of pipelines to bring cheaper natural gas and liquid fuel to large cities and may be further speeded by the adoption of modern mineral dressing methods to permit economical utilization of local raw materials. Our national resources of naturally high-grade silica sand are abundant, but most of the best deposits are situated so far from large centers of population that it now costs $3.00 to $5.00 a ton to carry the sand from the mine to the optimum site for a factory making beverage bottles, scientific and electrical glassware, and miscellaneous blown and pressed ware for local markets. It follows that on the basis of freight savings alone it may be economical to use material from inferior deposits closer to the factory even though the f.O.b. cost of mining and treatment may be much higher than at a higher grade deposit farther away. Particle-size distribution is a feature of glass-sand specifications. As long as glassmakers insisted upon having their sand principally coarser than 100-mesh, any material was automatically excluded from consideration that could not be purified without fine grinding or other drastic treatment which greatly reduces the size of the quartz grains. However, re- cent large-scale tests in Norway' showed that finely-crushed quartz used in a soda-lime-silica glass batch caused it to melt and become refined appreciably faster than when ordinary coarse (Belgian) sand was employed. Dust losses were negligible. Since the pre-war cost of sand was only 3 pct of the manufacturing cost of the glass, it was deemed economical to pay twice as much for crushed quartz because of the saving in wear and tear on the furnace walls. In the author's unverified opinion, sand ranging in size between 150 and 400-mesh would probably be superior to that in the more usual range of 20 to 100-mesh. Former objections to fine sand (other than dust) were doubtless fostered by the natural concentration of impurities in the finer sizes. Ordinarily the most objectionable, as well as the commonest, impurity from the standpoint of the manufacturer of any but the cheaper qualities of colored glass is iron. No natural sands are really pure silica. Even water-clear quartz crystals are likely to contain impurities in the form of solid solution as well as inclusions which cannot be eliminated except by chemical treatment that will break down the silica lattice. Pure white pegmatite quartz will usually analyze 0.01 pct or more of iron oxide, and ordinary vein quartz and the quartz grains in most

Jan 1, 1951

By Leslie C. Richards

The competitive position of producers of industrial minerals depends upon the delivered price of their product. Freight charges are a major factor in the sales to consumers. A comparison of freight rates on movements of limestone and silica rock in the Pacific Northwest shows a wide variance in mills per ton mile for like hauls, thereby favoring some localities over others. Introduction: Sooner or later the potential miner of industrial minerals reaches the conclusion that of the various factors he must consider, the marketing of his product is. the most important. The sooner he realizes this the better, as successful industrial mineral producers .will confirm. Herein lies a difference between i.ndustria1 mineral mining and metal mining. Often in the latter, technical problems of mining or concentrating are equal to or even surpass those of marketing. This is not meant to imply that there are no problems in mining and beneficiation of industrial minerals, but these usually are outweighed by the problem of marketing. Recentlv. an official of a nationally known corporation :i the elecl.ro-metallurgical industry made an industrial mineral survey in the Pacific Northwest. In the course of his investigation he interviewed producers and potential producers of the various industrial minerals scheduled for use in the plant now being constructed in this area. He stated that he was interested in only three factors: namely, (1) Can your product meet our specifications? (2) Are you able to supply our tonnage requirements? and (3) What will be the delivered price? If there are several sources of supply of sufficient grade and tonnage, as is often the case in the Northwest, then the third factor becomes the important and deciding one. While industrial minerals are usually sold f.0.b. cars with the freight being paid by the buyer, it is the delivered and riot the f.0.b. price that determines the competitive position of the producer and his industrial mineral product. Unfortunately for both the consumers and producers of industrial minerals in the Northwest, the sources are generally a considerable distance from the markets. This necessitates long rail hauls, for which transportation charges make up the largest share of the delivered cost and the delivered price of the product. Is it any wonder then, that rail rates play such an important part in the marketing of industrial minerals? In order to sell his product, the producer must be able to deliver to the market at a competitive price. It must be remembered that his largest cost factor is rail transportation, and that he is limited to markets that he can reach competitively. Since the cost of rail transportation is so important, let us compare various freight rates in the Northwest and attempt to determine their influence on marketing. A study of all rates on all industrial minerals transported in this area, is beyond the scope of this paper. For the purposes of comparison, let us consider limestone (broken, crushed, or ground), and silica rock. These are widely used industrial minerals, and are carried by several different rail routes from.the sources of supply to the centers of consumption in the Pacific Northwest. Markets and Sources of Supply: Limestone has a number of uses in western Oregon and Washington. Among them are agricultural lime for the soils of the Willamette Valley and southwestern Washington; paper rock for the mills in such cities as West Linn, Oregon City, Newberg, St. Helens, and Salem, Oregon, and Camas and Everett, Wash.; chemical and metallurgical-grade limestone for the metallurgical plants centering around Portland, and the Tacoma-Seattle areas'; and sugar rock for the sugar refineries at Toppenish, Wash., and Nyssa, Oregon. Since limestone for cement manufacture is generally processed near the quarry, transportation

Jan 1, 1951

By Leslie C. Richards

Sooner or later the potential miner of industrial minerals reaches the conclusion that of the various factors he must consider, the marketing of his product is. the most important. The sooner he realizes this the better, as successful industrial mineral producers .will confirm. Herein lies a difference between i.ndustria1 mineral mining and metal mining. Often in the latter, technical problems of mining or concentrating are equal to or even surpass those of marketing. This is not meant to imply that there are no problems in mining and beneficiation of industrial minerals, but these usually are outweighed by the problem of marketing. Recentlv. an official of a nationally known corporation :i the elecl.ro-metallurgical industry made an industrial mineral survey in the Pacific Northwest. In the course of his investigation he interviewed producers and potential producers of the various industrial minerals scheduled for use in the plant now being constructed in this area. He stated that he was interested in only three factors: namely, (1) Can your product meet our specifications? (2) Are you able to supply our tonnage requirements? and (3) What will be the delivered price? If there are several sources of supply of sufficient grade and tonnage, as is often the case in the Northwest, then the third factor becomes the important and deciding one. While industrial minerals are usually sold f.0.b. cars with the freight being paid by the buyer, it is the delivered and riot the f.0.b. price that determines the competitive position of the producer and his industrial mineral product. Unfortunately for both the consumers and producers of industrial minerals in the Northwest, the sources are generally a considerable distance from the markets. This necessitates long rail hauls, for which transportation charges make up the largest share of the delivered cost and the delivered price of the product. Is it any wonder then, that rail rates play such an important part in the marketing of industrial minerals? In order to sell his product, the producer must be able to deliver to the market at a competitive price. It must be remembered that his largest cost factor is rail transportation, and that he is limited to markets that he can reach competitively. Since the cost of rail transportation is so important, let us compare various freight rates in the Northwest and attempt to determine their influence on marketing. A study of all rates on all industrial minerals transported in this area, is beyond the scope of this paper. For the purposes of comparison, let us consider limestone (broken, crushed, or ground), and silica rock. These are widely used industrial minerals, and are carried by several different rail routes from.the sources of supply to the centers of consumption in the Pacific Northwest. Markets and Sources of Supply: Limestone has a number of uses in western Oregon and Washington. Among them are agricultural lime for the soils of the Willamette Valley and southwestern Washington; paper rock for the mills in such cities as West Linn, Oregon City, Newberg, St. Helens, and Salem, Oregon, and Camas and Everett, Wash.; chemical and metallurgical-grade limestone for the metallurgical plants centering around Portland, and the Tacoma-Seattle areas'; and sugar rock for the sugar refineries at Toppenish, Wash., and Nyssa, Oregon. Since limestone for cement manufacture is generally processed near the quarry, transportation

Jan 1, 1951

By A. E. Chute

The shortage of sulfur is not only continuing but appears to be worsening, attended by steadily rising prices. At the same time emphasis on air-pollution abatement is also increasing. These two factors, a rising market and the growth of environmental attention, have encouraged producers to carefully review all possible sulfur sources. As a result, production of sulfur from hydrogen sulfide occurring in petroleum is receiving greater attention than ever before. Until about a decade ago, the practice of recovering sulfur from hydrogen sulfide separated from gases (either found naturally or generated in desulfurization of liquid petroleum) was wide1y recognized but contributed little to total free-world sulfur production. However, during the past ten years, the production of sulfur from this source has increased so rapidly that it now accounts for a substantial portion of total production. This trend shows no signs of slackening, and current forecasts predict that recovered sulfur may become the dominant source of supply within ten years, exceeding mined sulfur production. This paper is intended to list sulfur sources and relationships, and to discuss the potential of producing sulfur from petroleum. The processing involved, in addition to product storage and transportation will also be discussed along with important economic aspects of sulfur recovered from hydrogen sulfide. For many years, most of the world's elemental sulfur has been produced from salt domes, predominantly by the Frasch process. During the past decade, however, another production source has developed so quickly that it is expected to surpass the Frasch production sources within a short time. This new source lies in the petroleum gases and liquids from which dramatically increasing quantities of elemental sulfur are being recovered. In the phraseology of the trade, the sulfur so obtained is know as "recovered sulfur," a term which does not, as one might expect, include sulfur recovered from other sources such as smelter gases. The growth rate of recovered sulfur compared to that of Frasch sulfur, total elemental sulfur, and total Free World sulfur in all forms is shown in Fig. 1 Since 1963, sulfur consumption has exceeded production,with the natural result that the price of sulfurhas continually increased. The posted price reported for f.o.b. Port Sulphur, La., has risen from as low as $18 per ton in 1962 to $32.50 per ton in mid-1967. With freight and other charges, delivered prices have of course run much higher, amounting to $45 or $46 per ton on the east and west coasts. In some cases, spot sales for as much as $60 have been reported. Although it is playing an ever-increasing role in the sulfur market, recovered sulfur was originally a by-product of the removal of hydrogen sulfide from natural and petroleum refinery gases. Today, however, it is often the most valuable product of a multi-product processing facility. Since there are two major sources of recovered sulfur—production and refining processes —natural gas is included with liquid petroleum for purposes of this discussion. Sulfur from these sources is produced in the form of gaseous hydrogen sulfide which is removed from a gas stream and converted to elemental sulfur. Gases in which hydrogen sulfide occurs naturally are natural gas and the gas produced from a high=pres-sure crude=oil or condensate field.

Jan 1, 1969

By Thomas P. Forbath

THE sudden realization that known sulphur reserves amenable to mining by the Frasch hot water process are nearing exhaustion focused attention on widely scattered surface deposits throughout the world. These deposits are not necessarily of lower sulphur content than ores located underneath Louisiana or Texas salt domes which usually average about 30 pct sulphur disseminated in limestone matrix. Their near surface occurrence, however, renders exploitation by the Frasch process impossible. As is well known, the Frasch process depends on the presence of 500 to 1000 ft of overburden and cap rock above the sulphur deposits to permit melting underground sulphur in place by diffusing hot water under pressures of 200 to 600 psig in the formation and raising the molten sulphur to surface by air lift. This process renders possible the production of pure sulphur which is 99.5 pct pure without any subsequent treatment. Surface deposits contain sulphur in the same range of concentrations as the salt dome deposits, i.e., from 10 to 50 pct sulphur, associated with various gangue materials such as silica, limestone, and gypsum. The pirincipal distinction, then, does not lie in the percentage of sulphur contained in the ore, but in the geological nature of the deposit. A recent study' of the world sulphur supply situation estimated 1950 sulphur production in the free world countries at 5.6 million long tons, of which the United States produced 5.2 million tons, or 93 pct of the total. While America's domestic needs alone would have been covered by national production, about 1.4 million tons were exported during the same year. Despite all the steps which are being taken to restrict use of elemental sulphur and to force the fullest possible development of alternate sulphur sources here and abroad, the deficit in elemental sulphur production will probably increase with time. As a result of intensive prospecting for oil throughout the Gulf Coast area discovery of significant new salt domes is held unlikely. With the growing scarcity of sulphur and what appears to be an inevitable rise in price, recovery from deposits not amenable to Frasch-process mining assumes greater economic importance. Untapped Reserves The most important deposits in this category are located in Sicily, where elemental sulphur occurs in Miocene limestone and gypsum formation. Sulphur content of these ores ranges from 12 to 50 pct with an estimated average of 26 pct. Although quantitative estimate of these reserves is not available it is held that they exceed 50 million tons of sulphur. Similar deposits occur also on the mainland which contribute about one-third of Italy's total current annual production of 230,000 tons, but these are known to be nearing exhaustion. Significant surface deposits of volcanic origin are located in South America, Japan and western United States, silica being characteristic gangue con-stituent. The largest of these deposits are in South America. More than 100 extend over a zone 3000 miles long, paralleling the west coast of South America. 'Total sulphur content of these deposits has been estimated to be as high as 100 million tons. The main islands of Japan also possess at least 40 known volcanic sulphur deposits with probable reserves of 25 to 50 million tons.' Prospected reserves in western United States might amount to 2 million long tons, principal deposits being located in the northwestern part of Wyoming, southern Utah, and eastern California. Volcanic deposits of lesser importance are found around the Mediterranean, in Turkey and Greece, and in Africa, Egypt, Abyssinia, and Somaliland. Beneficiation Methods Different methods of beneficiation have been used in these various locations. In Italy the Calcarone kiln and Gill regenerative furnaces are used exclusively. Both utilize heat liberated by burning part of the sulphur in the ore to liquify or vaporize the remaining sulphur, which is recovered by solidification or condensation. The Calcarone kiln is of conical shape, generally 35 ft in diam at base and 18 ft high. A kiln of 25,000 cu ft capacity burns for about two months and yields about 200 tons of sulphur. The Gill furnace consists of a series of chambers with domed roofs. Sulphur is burned and melted in one chamber at a time and the hot combustion gases are used to preheat the ore charge in the subsequent cell. These furnaces operate on a cycle of 4 to 8 days. The recovery yield of both systems is about 65 pct. Sulphur losses amount to 25 pct through the combustion to sulphur dioxide; about 10 pct is retained in discarded calcines. Ores containing less than 20 pct are not considered suitable as furnace feed. These methods are not only wasteful because of the low recovery obtained, but represent a serious atmospheric pollution problem. Sulphur produced ranges from 96 to 99 pct purity and thus does not match Texas or Louisiana sulphur. Owing to the present shortage, sulphur in the Middle East sells

Jan 1, 1954

By G. K. Engelhart

A multi-stage counterflow process developed in Germany preheats dry pulverized portland cement raw materials held in suspension in rotary kiln waste gases. Capacity of the first kiln installed for this purpose in the United States has been increased from 860 to 1500 bbl per day, with fuel reductions from 1,100,000 Btu to 650,000 or 700,000 Btu per bbl. Sixty percent of total waste gas is used. As full use of the gas stream is approached, additional kiln production and fuel economy may be expected. EFFECTIVE use of rotary kiln waste gases to preheat dry pulverized materials has been demonstrated in full-scale operation at the Allentown Portland Cement Co. plant, Evansville, Pa. Pulverized raw materials are preheated in suspension in the gas stream in a multi-stage counterflow process which draws the gases through a series of cyclone collectors. Upon entering the first cyclone stage the material, continuously delivered and suspended in the gas stream, is successively collected and re-suspended until it discharges through the kiln feed pipe. Gas and material contact time is thus prolonged, providing a high degree of heat recuperation with a very low temperature differential between gas and material at the final stage. The suspension preheater, developed by Klock-ner-Humboldt-Deutz AG of Cologne, Germany, was first installed at the Norddeutsche Huette plant, Oslebshausen, Germany. Similar preheaters are now in operation at three other German cement plants. The first American installation, at the Allentown Portland Cement Co. plant, was designed and manufactured by Fuller Co. of Catasauqua, Pa., Humboldt's licensee for the United States, Canada, and Mexico. Design of this installation is essentially the same as the German original, but provision was made for varying the method to adapt the process to specific objectives of American portland cement production. Differences between German and American cement clinker production practices are directly related to differences in three primary production cost items: fuel, labor, and power. Because fuel costs are high in Germany and elsewhere in Europe, thermal efficiency has been the first objective of European cement producers and manufacturers of rotary kilns. The Germans have developed such recuperative equipment as the present suspension preheater, the Miag calcinator, and the Lepol kiln, the invention of 0. G. Lellep. In North America labor is the principal cost item, although rising fuel costs are of growing concern. High clinker production is therefore of first importance. Recent installations of longer dry process cement kilns have been disappointing, failing to make satisfactory reductions in exit gas temperatures when production is held at an acceptable level. The Humboldt suspension preheater satisfies both

Jan 1, 1955

By Leon Merker

FLAME fusion growth of strontium titanate crystals was undertaken to obtain large transparent crystals on which physical data could be gathered. The fact that strontium titanate is a cubic crystal and probably has a high index of refraction indicated that it might be useful in optics. No large boules* of strontium titanate had been synthesized previously, and none have been found as natural occurrences. The flame fusion process, invented by Verneuil in 1904,1 was first applied to grow large crystals of ruby and has since been used extensively to grow crystals of corundum and spinel on a commercial scale. Only during the past nine years has this technique been applied to the growth of large single crystals of other high melting compounds such as rutile,2 mullite,3 and ferrites4 One of several significant advantages of the flame fusion technique over more conventional methods of growing crystals from a melt is that the crystals are grown without the use of melt containers. This fact alone excludes other methods of growing crystals from a melt whenever there are compounds with a melting point near 2000°C or above. Growth of the crystal, similar to that of a stalagmite, takes place inside a circular refractory furnace that does not contact the crystal, Fig. 1. This eliminates a serious source of impurities as well as the likelihood of multi-crystalline solidification along the container walls. The flame fusion technique is particularly advantageous for research because it produces large crystals quickly and at lower cost. A corundum crystal 25 mm long and 12 mm in diam can be grown in 2 to 3 hr. Operating conditions permit observation of the growing crystal during any stage of the process. The various flame patterns and a wide range of oxidation-reduction conditions can be investigated in a relatively short time. It should be pointed out that formation of the foot of the boule is the most critical step in growing an unfractured boule. When the tip of the sintered cone is fused to initiate crystal growth, the original area of fusion should be kept as small as possible so that one crystallite can assume dominance over all the others and propagate as a single crystal. If the boule start happens to consist of several crystals, usually the entire boule also contains several crystals. In many cases these tightly cohering crystals exhibit different crystallographic orientations. Although the basic technique of the original Verneuil process has been retained, refinements in method and burner design have been developed in recent years. For example, boule growth may be initiated on a seed crystal rather than by fusion of a sintered cone. The danger of multicrystalline or twinned boule starts is thus eliminated, and this procedure may also be used to grow boules of predetermined crystallographic orientation. Prior Art: Of the many attempts to produce artificial gem crystals, most early efforts% ere directed toward synthesis of .rubies and sapphires and diamonds. None of these efforts resulted in a process that was commercially practical. Without exception only tiny crystals of corundum were obtained, and those at excessive cost. Verneuil announced his process in 1904; Ravier6 in 1934 presented a detailed description of a commercial boule production plant. Descriptions of the German synthetic stone industry, the process details, and the equipment used have been published by Barnes7 and by Merker.'

Jan 1, 1956

By L. R. Blair

Many hydrated silicates have been synthesized and sold for commercial use. However, this paper discusses only hydrated calcium silicates and, to a lesser extent, hydrated magnesium silicates. Synthetic calcium silicates were first formed by man when he found that mixtures of silica or silicates and lime in water set up to form cements. The material which was responsible for the cementing properties was calcium silicate hydrate, although this fact was not recognized until early in this century. In the early 19001s, synthetic calcium silicates, reinforced with fibers and formed simply by reacting calcium hydroxide and silica in water with fiber at atmospheric or under low pressure autoclave conditions, found increased use in thermal insulations and in building products. These insulations were found to have a low thermal conductivity and would withstand temperatures up to 650°C. This, combined with their very low densities (from 8 to 50 Ib per cu ft) and fairly high strength, also made them suitable for use as building products. Following the disastrous Morro Castle fire of the 1930Js, calcium silicate board products were used as partitioning material in all shipboard construction in the U.S. As autoclaving techniques were improved and developed, it was: learned that under hydrothermal conditions new and useful calcium silicates which could be used under more extreme temperatures (up to 980' C) could be prepared. These had high surface areas and other unique properties which suited them for use as fillers, pesticide carriers, low temperature insulating materials, and adsorbents for the removal of fatty acids from various solutions. Hydrated magnesium silicates have not been studied as extensively as the calcium compounds. Their first important use was in the filtration of dry cleaning solutions for the removal of fatty acids. With the introduction of detergents, it was found that these products lost their advantage because of their high affinity for the detergent chemicals. However, in recent years these chemicals are finding increasing use as decolorizing agents for fats and anti-caking agents for resins. Some materials with very high surface are finding new use as adsorbents. CALCIUM SILICATE HYDRATE COMPOUNDS AND THElR CONDITIONS OF FORMATION Within the past ten years much has been done in the field of calcium silicate hydrate chemistry. As a result of this work it has been found that at least 25 different forms of calcium silicate hydrate can either be formed synthetically or found as naturally occurring materials. The stability and composition relationships among these 25 compounds present a very complicated picture, and many of these very closely resemble other forms and are difficult to dis-

Jan 1, 1962

By Arthur Tauber, Horst Kedesdy

FERRITES are sintered metallic oxides of the spinel structure type1 and belong to the class of soft ferromagnetic materials. Similar to a ceramic, they can be formed and fired to a dense body, exhibiting a high electrical volume resistivity ranging from 10 90 10' ohm-cm as compared with 10-6 hm-cm for some of the metallic magnetic materials. This high resistivity, with resulting low eddy current losses, finds special application at high frequencies. The dispersive susceptibility of ferrites at microwave frequencies has also led to many applications in this field. Where high resistivity with high permeability is desirable, ferrites are used in low frequency applications. During the last few years ferrites exhibiting rectangular hysteresis loops have been developed for computer and magnetic memory systems. The general formula for ferrites is MeFe2O4 where Me is a divalent metal ion such as Ni, Zn, Mg, Mn, Cu, Cd, and Fe. Only two of these ferrites are nonferromagnetic, namely, those with Zn and Cd. Solid solutions can be formed between different ferrites, and it is of interest to note that solid solutions of a ferromagnetic ferrite with a nonferromagnetic ferrite yield much better magnetic materials than the basic ferrite body. In general, it can be said that the solid solution formation between ferrites has widened the field of ferrite synthesis and has led to methods of preparing materials with a large variety of magnetic properties. During the last two decades the synthesis of ferromagnetic oxides has been the object of extensive research, but commercial production has been started only within the last ten years. Along with more fundamental studies, there remains the never- ending task of developing ways to realize the optimum characteristics of materials in large-scale production. Ordinarily, to produce a ferrite material it is necessary for the constituent oxides to be mixed intimately, pressed, and then fired at temperatures above 1000°C. Ferrite Synthesis: Formation of a basic ferrite by solid state reaction from Fe,O, and a monoxide such as NiO, under normal atmospheric conditions, is governed by a progressive diffusion of cations between adjacent particles of the constituents. Firing temperature, furnace atmosphere, and cooling can vary the magnetic properties, however. If, for example, a dioxide, a sesquioxide, or an oxide of the Me0 type is substituted for the monoxide, the reaction mechanism becomes more complex and extremely dependent on atmospheric conditions and firing cycles. For this reason reproduction often

Jan 1, 1958

By K. W. Smith, E. A. Thomas

Various grades of synthetic mullite have been developed in recent years to replace or supplement natural sources of mullite deriued from the mullite group of minerals consisting of sillimanite, kyanite, and andalusite. Raw materials and heat treating processes used in making synthetic mullite are described. Chemical and physical data are given for typical grades and crystalline structure is illustrated with micrographs. Use of synthetic mullite as a refractory material in the glass and metallurgical industries is discussed. Mullite (3A12O3.2siO2), the only stable compound formed in the alumina-silica system, is usually present to some degree in all aluminum silicate ceramic products. The formation of mullite is considered beneficial to give rigidity to the structure and is dependent upon the ratio of Al2O3 to SiO2 in the original composition, particle size, degree of mixing, firing temperature, cooling rate, and the presence of auxiliary glass-forming fluxes. Mullite may also be formed at the reaction interface of fire clay or alumina-type refractories in contact with glass or slag melts. The term synthetic mullite is commonly used today to identify a class of sintered and fused aggregates or grains in the alumina-silica system having a highly developed mullite structure but derived mainly from raw materials other than the sillimanite group of minerals. Within the past 15 years extensive research has been done to develop economical processes to form sintered synthetic mullite aggregate to replace calcined Indian kyanite in super-refractories. Severa1 brands of such mullite are now being produced in commerical quantity and finding extensive use in refractories. Based on the service results of such refractories in many applications throughout the metallurgical, ceramic, and glass industry these developments have been considered successful and suitable substitutes for Indian kyanite now appear assured. EARLY DEVELOPMENT The conversion of kyanite, sillimanite and anda-lusite minerals of the sillimanite group to mullite and their use in refractories and porcelain have been discussed quite extensively in the literature by peck,' Grieg,' Riddle and Foster,3 Bowen and Grieg,4 and others and will only be mentioned here for reference to compare properties with synthetic mullite. In 1928, curtis5 reported on the development of a high temperature gas-converter process for forming synthetic mullite. The raw materials were derived mainly from lumps of high alumina clay of the correct natural composition or blends of clays and alumina that was interground and briquetted to form a suitable charge to maintain a surface combustion firing within the converter. Curtis was, no doubt, the first to illustrate by micrographs in natural color the crystalline structure of mullite derived from kyanite and mullite derived by sintering clay and alumina mixtures at temperatures above cone 32 (3123°F) and by electric fusion. In 1937, sei16 was issued a patent covering the use of a mixture of alumina-silica minerals and alumina in the proportion to form a mullite-yielding material at temperatures in excess of 3100' F. During the period from 1930 to 1940, economic conditions were not favorable for the production of synthetic mullite mainly due to an adequate supply of good grades of Indian kyanite ore suitable for conversion to mullite. Uncertain conditions on availability of the Indian kyanite during the early stages of World War II fostered further study on the development of synthetic substitutes. In 1943, McVay and wilson7 reported on an extensive investigation of domestic substitute materials. Their work covered essentially the use of mixtures of electric furnace mullite, calcined topaz, and calcined domestic kyanite. Compositions were found that gave equivalent or better hot load strength than Indian kyanite in mullite-type brick compositions; however, the calcining of the topaz presented certain physical and chemical problems on the disposition of silicofluoride and hydrofluoric acid while the high cost of electric furnace mullite was a limiting factor. In this work it was pointed out that water-quenched fused mullite was found to be unstable on reheat and gave poor hot load strength due to excessive glass present whereas the slow cooled or annealed mullite contained large crystals of mullite and corundum with little glass and gave superior results.

Jan 1, 1961

By W. W. Mein

IN March 1949 the Calaveras Cement Co. was sued by five landowners whose properties are located in the vicinity of the plant. These landowners—all of them cattle ranchers—sued for dust damages of $120,338 and for an injunction preventing the company from casting dust upon their properties in injurious quantities. The issue was split, the jury deciding the amount of damages and the court handling the injunction features. The action came to trial before a jury in April of that year and resulted in damages being awarded in the amount of $7,508. A month later the court issued its injunction requiring recovery of stack dust to an 87 pct minimum. The Calaveras plant, shown in Fig. 1, is located three miles from San Andreas in the heart of the Mother Lode country, about 45 miles east of Stockton, Calif. Since it is in a small town, the company's responsibilities to its employees and to the community are different from those of plants located in large centers of population. Construction of the plant was begun in 1925, and production was started the following year. Standard gray Portland cement as well as several specialty cements are produced. Production facilities have been continually enlarged so that the present capacity is more than double what it was 25 years, ago. The most important item in the company's expansion program was the purchase in 1945 of an 11 ft 3 in. x 360 ft Allis-Chalmers kiln which had been declared surplus by the Defense Plant Corp. The company is now able to produce about 2,500,000 bbl of cement a year, and employment at the plant is approximately 300. The production of cement has always involved a dust problem, solution of which has been attempted in a number of different ways. By far the most efficient method of catching dust discharge is electric precipitation. Soon after the company went into production in the 1920's, the landowners near the plant began complaining about dust discharge. The company settled the matter by paying them a total of $27,000 for dust damages incurred during the period from 1929 to 1938. In the latter year the two-unit Cot-trell Electric Precipitator shown in Fig. 2 was installed and collected over 85 pct of the dust resulting from operation of the two 11 ft 3 in. x 10 ft x 240 in. kilns. From 1938 until 1946 the landowners registered no objection and were apparently satisfied with that dust recovery. In 1946, however, the substantially higher production resulting from operation of the new kiln immediately overtaxed the facilities of the existing two-unit precipitator. In a short time claims for dust damages were again received from the landowners. The company informed them that because of postwar shortages it would take several years to install a new precipitator. The company stated that it intended to purchase an additional precipitator and offered in the meanwhile to pay the landowners a fair amount to cover their damages. This offer was rejected and the landowners filed suit in the Superior Court of Calaveras County asking for total damages of $120,-338 and for the injunction outlined above. Case for the Ranchers The attorneys for the plaintiffs produced three different types of witnesses: first, the landowners themselves and members of their families; second, other cattle raisers who were sympathetic to the plaintiffs; and third, several types of technical experts: veterinarians, soil chemists, and an aerial photographer. The testimony of these witnesses was designed to establish that the flue dust from the plant had not only damaged the land and the forage, but had also caused fluorine poisoning to their animals. By a combination of these causes, the plaintiffs attempted to prove substantial loss of profits.

Jan 1, 1952

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

The Grand Isle sulfur mine is located in the Gulf of Mexico, approximately seven miles off the coast of Grand Isle, Jefferson Parish, La. The deposit is on acreage covered by oil, gas, and mineral leases originally issued in favor of Humble Oil & Refining Co. by the State of Louisiana which were continued, maintained, and redesignated by the U.S. Department of the Interior after passage of the Outer Continental Shelf Lands Act. The sulfur deposit was discovered in 1949 when Humble Oil & Refining Co. penetrated more than 200 ft of sulfur-bearing limestone in a zone between 1813 and 2075 ft below sea level. In 1954, Humble drilled ten more sulfur prospect holes, eight of which encountered sulfur ore. On September 19, 1956, Freeport Sulphur Co. acquired from Humble Oil & Refining Co, the sulfur rights underlying the tracts, and the actual design of the installation began the same month. The first structural contract was awarded in December 1957 and offshore erection began in June 1958. The initial phase of construction has been completed and production by the Frasch process commenced in April 1960. The estimated total cost of the project is $30 million, of which $8 million is the extra cost incurred by the necessity of offshore operations. More than $22 million was expended before production was started. GEOLOGY OF DEPOSIT Grand Isle is the third largest sulfur deposit in the U.S. The orebody embraces several hundred acres, but its outer limits are yet to be defined to the northeast, east, and south. Most Gulf Coast sulfur deposits occur in a caprock mantle of calcite (referred to as limestone), anhydrite, and occasionally gypsum, which covers the apex of an intrusive mass of salt. Commercial quantities of sulfur are usually confined to the calcite or limestone member. Most often such limestone is completely enclosed by dense anhydrite below and impervious sediments above, which effectively form a closed reservoir. The depth of the Grand Isle orebody ranges from 1800 ft to 2500 ft below sea level. Within the present boundary, the sulfur-bearing limestone varies in thickness from 220 ft to 425 ft, while the sulfur content varies an average of about 15 pct in the leanest hole to an average of about 30 pct in the richest. Rock containing less than 5 pct sulfur is not classed as ore, and holes assaying less than 20,-000 long tons per acre of sulfur in place are not considered commercial offshore. The sulfur enrich-

Jan 1, 1961

By Howard A. Meyerhoff

In western Argentina, in the Province of Mendoza and the Territory of Neuquen, there is a series of solid bitumen deposits which are claimed to be the most extensive in the world. In a linear belt 500 km (311 miles) long, roughly paralleling the axis of the Andes but occupying a variety of positions with respect to the orogenic structures, more than 100 outcrops have been reported. Approximately 70 of these have been prospected, and some mining has been planned or attempted for about half this number. Limited tonnage, high sulphur content, inaccessibility, labor shortages, and disastrous fires have taken a heavy toll among these operations, and in 1947, only 4 deposits were being actively mined, but 8 more were being explored and developed with a view to placing them in production. Inasmuch as these deposits are currently yielding a substantial fraction of Argentina's limited domestic supply of solid fuels, a brief account of the deposits and of the small industry based upon them will provide a commentary on Argentina's fuel problem. Character of Solid Bitumens The solid bitumens of Mendoza and Neuquen are petroleum derivatives, as is indicated by the following ultimate analysis : Constituents Per Cent Hydrogen.................... 6.8 Carbon...................... 82.4 Nitrogen..................... 1.6 Oxygen...................... 2.7 Sulphur...................... 2.2 Ash.......................... 4.3 100. 0 In physical appearance they bear a close resemblance to coal and are commonly called carbon. Their specific gravity has an extreme range of 1.10 to 1.777 in 36 samples weighed, but the average is between 1.14 and 1.24. The material is black, lustrous to dull, with blocky to sub-con-choidal fracture. Though brittle, the purest material is softer than anthracite and exhibits slightly more cohesion. This bituminous material is generally known as asfaltita or asphaltite, but definitive chemical studies indicate that the term asphaltite or grahamite can be applied correctly only to the exceptionally pure material of the Auca Mahuida district in Neuquen. Some other name should be used for the chemically variable bitumens found in all other districts, and the designation "asphaltitic pyrobitumen" has been proposed by Carlos A. S. Piscione.1 At the present time these bitumens are finding favor as solid fuel and as a gas-producing medium. They yield heat values of 8650 to 9750 cal,2 or 14,500 to 16,750 Btu per pound, and in consequence of their excellent heating qualities and the scarcity of imported coal, they are marketed as far away as Buenos Aires at a price of go to 95 pesos, or approximately $22 to 23, per metric ton. In burning, the material swells and decomposes into solid, fluid, and gaseous fractions which burn violently though nonexplosively. Its combustibility has been responsible for disasters and virtually complete destruction at Mina La Es-peranza and Mina Santa Marta, and for minor mishaps elsewhere, as at Mina Escondida in August 1947.

Jan 1, 1949