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By William J. Shampine

The Floridan aquifer, which underlies all of Florida, yields water with a sulfate content of less than 50 parts per million in the north-western part and throughout most of the center of the State. In the southern part of Florida and along the most of the east coast, the sulfate concentration generally exceeds 100 parts per million and is as much as 1,700 parts per million. The sulfate concentration tends to be higher in the deeper zones of the aquifer. This map shows the sulfate concentration in the upper part of the aquifer. Sulfate is found in almost all natural water. Sulfate in rainwater is dissolved from impurities and gases in the atmosphere. Rankama and Sahama (1955, p. 314) report that the average sulfate content of rainwater is two parts per million; however, concentrations have been as high as 283 parts per million. Much of the sulfate in rainwater comes from hydrogen sulfide gas which is generated in shallow water on the continental shelves. The combustion of bituminous coal used for heating and industrial purposes seems to be an important local source of sulfate.

Jan 1, 1966

By L. B. Pankratzt

The heat capacity of dimo1ybdenum carbide (Mo2C) was measured from 51° to 298° K, and the entropy at 298.15° K was evaluated. Heat content measurements above 298.15° It were conducted for dimolybdenum carbide (M0caY) and monotantalum carbide (TaC). The results were combined with known heats of formation and the 298.15° K entropy for TaC to obtain values of the heat and free energy of formation from 298.15° K to 1,400° K for MoaC and from 298.15°K to 1,800° K for TaC.

Jan 1, 1966

By Walter Kawa

Coals of various rank were reacted by the Bureau of Nines in plasma jets generated from argon and argon-hydrogen mixtures containing up to 33 volume-percent hydrogen. Average plasma temperatures ranged from about 3,400° to 12,000° C. Products were a solid residue and a gas containing hydrogen, methane, acetylene, diacetylene, and oxides of carbon. The highest yield of acetylene obtained with argon plasmas was 15 percent by weight of moisture- and ash-free coal. The data indicated that acetylene yields of 40 percent or higher can be obtained from the reaction of coal in argon-hydrogen plasmas, although results from these experiments could not be correlated with operating variables because of low recoveries plasma contained sufficient energy to heat the coal to temperatures as high 9,000 or 10,000° C, but complete devolatilization did not occur in any experiment.

Jan 1, 1966

By R. B. Roberts, A. L. Mular

A simple way to determine the IEP of oxide minerals is described. The method is shown to apply for fine powders of Fe203 and ZnO. The IEP lies at pH 6.95 for Fe203 and at pH 9.08 for ZnO.

Jan 1, 1966

By Donald R. Corson

The Bureau of Mines is conducting research on the effects of various established and potential soil-stabilization additives to hydraulic backfill. This initial phase is an evaluation of the effect of inclusion of varying amounts of Portland cement and combinations of cement and a dispersant on the bearing strength of backfill. Results of unconfined compression tests are given for over 200 sample cylinders incorporating a fill material with cement or cement and dispersant. Inclusion of a minor amount of dispersant (0.2 percent by weight) is found to yield a significant increase in strength for 20-to-1 and leaner sand-cement mixes. An apparent optimum concentration of dispersant exists beyond which no further increase in strength is achieved. A dispersant-cement ratio of l.8- to-1 yielded a strength increase of 515 percent over the strength of untreated 40-to-l sand-cement mixes.

Jan 1, 1966

By C. D. Stahl, S. M. Farouq Ali

This investigation attempts to describe and simulate the alcohol displacement process by means of a cell model, as employed in chemical engineering practice. The proposed model is more simple than previously proposed models. and utilizes parameters chosen on a theoretical basis. The model successfully reproduced the formation of the stabilized bank and the breakthrough of alcohol, the latter depending on one of the model parameters, which may be correlated with the length of the porous medium. Moreover, the effects of the phase behavior of the liquid system involved, as observed in experimental studies, were reproduced. Several variations of the basic model were devised and tested on a digital computer. These included the cases in which: (1) the actual value of fractional flow was used in cell-to-cell computations; (2) the number of cells was varied within the same run; and (3) incomplete rather than complete phase equilibrium was assumed within each cell. The proposed cell model clarifies the basic mechanism of the process. Detailed concentration profiles obtained for each cell, for instance, showed the mechanism of bank formation in relation to the phase behavior characteristics. The results obtained indicated a varying degree of phase equilibrium concommitant with changes in the velocities of the phases in an actual alcohol displacement. This condition was approximated by changing the number of cells during the simulation. Interesting information was obtained on the influence of path length on the efficiency of alcohol displacement, which has been the subject of some controversy. Certain limitations preclude the use of the proposed model as a substitute for experimental studies. The results obtained were, nevertheless, of value in interpreting the experimental results. INTRODUCTION During recent years considerable effort has been directed toward an understanding of alcohol displacement, the process whereby oil and water are recovered from a porous medium by the continuous injection of a solvent. The complex nature of the physical process involved has so far defied a complete mathematical treatment. Other methods of approach, amounting to an overall material balance, have been proposed, yielding useful information on certain aspects of the process.1-3 Taber et al, in particular, defined the displacement mechanism in terms of the phase behavior of the alcohol-oil-brine system invoIved.2 Wachmann reported a mathematical treatment of alcohol displacement subject to certain simplifying assumptions? Donohue proposed the use of a "cell model" for simulating alcohol disPlacement.5 The nature of the assumptions involved limited the utility of the model. The present work attempts to examine the variables involved in the simulation of alcohol displacement and discusses several possible versions of the basic cell model. Under certain conditions the model results are similar to the experimental results. In particular, the spontaneous formation of of the stabilized bank and the effects of the system phase behavior were successfully reproduced. PREVIOUS WORK ON CELL MODELS Cell models and the theoretical plate concept are often used in solving chemical engineering problems in which an explicit mathematical solution may be difficult or impossible to obtain. Examples of such applications occur in distillation, gas-liquid chroma tography,6 reactor technology, absorption, etc. In petroleum engineering, such a model was used by Attra7 to describe non-equilibrium gas drive, and by Higgins and Leigh ton8 to calculate sweep efficiency in water flooding. Aris and Amundsen pointed out the equivalence between the diffusion model and perfectly mixed cells connected in series.9 Deans proposed a three-parameter cell model to simulate two-component

Jan 1, 1966

By James F. Devine

The radial, vertical, and transverse components of particle velocity were recorded by Bureau of Mines investigators along gage arrays extending in one or two directions for 145 to 3,170 feet at five quarries. Of the 39 quarry blasts, 12 were instantaneous blasts, 5 were of the one hole per delay type, using millisecond delayed caps, and 22 were multiple hole per delay type employing millisecond delay detonating fuse connectors. Charge weight per hole ranged from 8 to 1,500 pounds, and the charge weight per delay interval, including the instantaneous blasts, ranged from 25 to 4,620 pounds.

Jan 1, 1966

By Martin H. Stanezyk

The Bureau of Mines investigated leaching of selected copper sulfide minerals and a composite of impure flotation concentrates at elevated temperatures and pressures with ammoniacal solutions. Copper 1 (tractions of 96 percent were obtained by leaching chalcopyrite at 75° C under oxidizing conditions for 60 minutes. An extraction of 99 percent of the copper contained in the composite concentrate was obtained by leaching the product for 90 minutes at 75° C. In tests of bornite, chalcocite, and covellite, 90 to 97 percent of the copper was extracted at 20° C provided an 8-hour reaction period was used. At 75° C essentially complete dissolution of the copper from these three minerals was accomplished in 60 minutes. Additions of ammonium sulfate to the leach solutions were required to obtain high-percentage extractions of the copper from bornite, chalcocite, and covellite. Although ammonium sulfate was not required when digesting chalcopyrite, copper extraction was enhanced and less free ammonia was required when ammonium sulfate was added to the leach pulps. The chemistry of leaching copper minerals was studied. It was C, termined that chalcocite altered to covellite as one step in the dissolution When leaching iron-bearing copper sulfides, hydrated iron oxide formed on the mineral surfaces, indicating that a diffusion process prevailed. No evidence of covellite was detected.

Jan 1, 1966

By John A. Ames

Limestone for portland cement must be beneficiated to produce uniform raw material for the kiln. Careful quarrying and selective recovery are factors in this process, but the chief aspects of beneficiation are "in plant" processes, such as crushing and screening, washing, grinding, flotation, and heavy-media separation. Numerous technical and economic problems exist. Detailed studies of the limestone deposit and the stone itself are required for intelligent beneficiation. As used in this paper, beneficiation is defined as the improving of limestone composition so as to produce an economically usable raw material A limestone deposit is defined as a mass of limestone which can be recovered, by quarrying or mining, for sale or for use in a commercially profitable operation. The stone may require elaborate processing, or it may qualify with little or none. Obviously, the "commercially profitable" qualification may change as the economy changes. Potentially commercial deposits may be of much better quality than actually developed deposits, and yet may be denied development for various economic reasons.

Jan 1, 1966

By Reynold Q. Shotts

A study was made of the coal resources of an area in Jackson County, Ala., forming a part of the Flat Rock, Henegar, and Stevenson quadrangles. The area studied is a portion of the Plateau coalfield on Sand Mountain and is near the Tennessee Valley Authority's Widows Creek steamplant. Since no detailed geological study of this area had been published, some reconnaissance work was done. The coalbeds and adjacent strata such as sandstones, conglomeratic sandstones, and conglomerates were studied. Available drill logs, together with the areal geology, provided sufficient information to permit correlation of the coalbeds and an estimation of coal reserves. For all categories of reserves, computed on a regional basis, a total of 72,920,000 tons of coal more than 14 inches thick is estimated for the areas studied in Stevenson, Flat Rock, and Henegar quadrangles. Of this tonnage, 40,001,000 tons is estimated to have less than 60 feet of overburden. The total measured coal reserves for the above three quadrangles are 16,359,000 tons, with 12,411,000 tons under less than 60 feet of cover.

Jan 1, 1966

By R. F. Nielsen, R. G. Bentsen

Jan 1, 1966

By R. L. Hopkins

Fifteen alkyl cycloalkyl sulfides and three dicycloalkyl sulfides were synthesized to provide reference compounds in the search for these classes of sulfur compounds in crude oils. In synthesizing sulfides by alkaline alkylation the order in which the reactants were added was shown to determine the yield and purity of the product.

Jan 1, 1966

By H. C. Fuller

Submerged combustion and inverse solubility methods were investigated as promising alternative means for crystallizing manganese sulfate from solutions produced by leaching manganese ores with either sulfuric acid or sulfur dioxide. Evaporation of water from typical manganese sulfate solutions by sub-merged combustion techniques enabled production of a slurry containing 32 to 39 pct MnSO4.H2O crystals suspended in a saturated solution of manganese sulfate. Such a slurry required further processing by thickening or filtration and drying to produce crystals of MnSO4.H2O. In a second approach, semicontinuous processing of manganese sulfate solu¬tions by thermal crystallization under pressure effected a recovery of 94.5 pct of the MnSO4.H2O as dry free-flowing crystals. Treatment of a solution containing about 100 grams manganese per liter at 189° C, produced a "barren" solution containing only 1.9 grams manganese per liter. Calculations made on comparable manganese sulfate solutions show that the heat requirement of the thermal crystallization method was about one-third to one-fourth that of the submerged combustion method.

Jan 1, 1966

By W. K. Coughlan

The Wabana deposit of Dosco Industries Limited is situated on the east coast of Newfoundland, at Bell Island in Conception Bay. It is a Clinton-type iron-formation of Lower Ordovician age. Five separate beds have been recognized, with others noted locally. Economic production has been obtained from the Lower, Middle and Upper beds, which are second, third and fifth in sequence, al-though at present only the Lower Bed is worked. The potential area of occurrence is about 70 square miles. It i;; bounded by major faults to the north, east and west and truncated by erosion at the south, where rocks of the de-posit crop out on the north side of the island. The iron is contained in oolitic hematite and chamosite, with minor siderite. As the deposit is submarine, conventional exploration methods are not applicable and much interpretation and projection from mined areas is necessary to guide exploration and development. With the interpretation of information from existing mined ores, it is possible, using a minimum of diamond drilling in advance of working faces, to maintain adequate ore reserves.

Jan 1, 1966

By J. A. Cavallaro

The heats of formation of anhydrous barium carbonate (witherite), strontium carbonate (strontianite), and lead carbonate (cerussite) were determined by solution calorimetry. The solution mediums were hydrochloric acid for barium and strontium carbonates and perchloric acid for lead carbonate. The heats of formation at 298.15° K are as follows: BaCO3 -297.5 ± 0.8 kcal/mole; SrCO3 -294.6 ± 0.5 kcal/mole; and PbCO3 -168.0 ± 0.3 kcal/mole.

Jan 1, 1966

By R. D. Vaughn

The analysis of laminar flow of power-law non-Newtonian fluids in narrow, eccentric annuli is employed in this paper to discuss the problems of lubricant flow in journa! bearings and of errors introduced by eccentricity in experimental studies with concentric annuli on extruders and wellbore annuli. The velocity profile and pressure loss-flow rate equations are developed for the laminar flow region. In addition, the expected error in flow rate and pressure-loss measurements for concentric annuli as a result of eccentricity is determined. For example, a 10 per cent displacement of the core of an almost concentric annul us would cause a 1.8 per cent decrease in the observed pressure loss for a fluid with a power-law exponent n of 0.25. The corresponding increase in the observed volumetric flow rate would be 7. 5 per cent. INTRODUCTION Non-Newtonianism and eccentricity occur simultaneously in two engineering problems: (1) flow of lubricants in journal-bearings and pressure-reducing bushings, and (2) flow of non-Newtonian fluids in plastic extruders and wellbore annuli. The lubricants used for moving parts are often non-Newtonian in character — often they are plastic in behavior. A solution to the problem of flow of non-Newtonian fluids in narrow eccentric annuli is particularly pertinent to this problem. In all experimental studies of laminar flow of fluids in concentric annuli, such as in extruders and well casings, the error due to eccentricity must be estimated or studied. A number of publicationsl-4,6,7 have dealt with this problem for Newtonian fluids; however, I am not aware of work for non-Newtonian fluids. This work is directed to the non-Newtonian problem. Before the solution to the problem is given, the pertinent conclusions from the work on Newtonian fluids will be reviewed. Heyda 1 and Redberger and Charles 2 have published general solutions to the problem of the laminar flow of Newtonian fluids in eccentric annuli, apparently without knowing of the earlier work of Ca ld well 3 and Bairstow and Berry,4 which is reported by Dryden, et al. 5 Although several mathematical routes are encompassed by the work of these authors, the results appear to be equivalent. Redberger and Charles2 show that the error caused by eccentricity in concentric annuli is negligible for small diameter ratios (k < 0.5); however, for large diameter ratios (k + l), the error in the predicted flow rate can be as great as 100 per cent or more. Partial solutions to the problem are available from the work of Dryden,5 Tao and Donovan6 and Piercy, et a1.7 Tao and Donovan examined the case of flow in narrow, eccentric annuli (k + 1) with and without rotation of the annular core. These authors also reviewed previous work on this subject and verified their approach with experimental data. Dryden gives the solution for the limiting case of complete eccentricity or tangency. Piercy, et a l. published an early solution to the problem of narrow eccentric annular flow. The conclusions of Redberger and Charles2 and the experimental proof of Tao and Donovan6 both suggest that the region of large diameter ratios (k + 1) is of main interest and that the parallel planes approximation to the solution in this region is satisfactory. This method will now be extended to the laminar flow of non-Newtonian fluids in narrow eccentric annuli. THEORETICAL SOLUTION The geometrical aspects of the problem are illustrated in Fig. 1. To represent the non-Newtonian fluid the power-law model was selected. This model has many disadvantages which have been pointed out; nevertheless, its simplicity, its frequent and wide applicability justify its use in this work. Fredrickson and Bird8 and Savins9 have used it as a basis for a theoretical study of laminar flow of non-Newtonian fluids in concentric annuli.

Jan 1, 1966

By Harry R. Nicholls

Preliminary tests on presplitting rock in the presence of an in situ static stress field were undertaken to study the influence of a horizontal static stress field on the creation of a vertical presplit fracture plane. These tests indicated that it is easier to fracture the rock parallel to the in situ maximum compressive stress than in other directions. Instrumented shots indicate that the interaction of stress waves generated by the detonating charges is probably responsible for starting tensile fractures between shotholes and that expanding gases may propagate these initial cracks by a wedging action. The hole spacing for presplitting appears to be equal to the half wavelength of the stress wave. However, wider hole spacing appears feasible if the initial fracture is started by closer hole spacing.

Jan 1, 1966

By Donald W. Mitchell

Certification tests for urethane-foam systems and techniques for apply-ing foam safely in mines are described. Fire hazard from foam exists if flame propagates beyond the ignition source or penetrates the foam. Foam that passes the certification tests can be applied on stoppings, continuous sections of ribs of relatively wide passageways (with no foam on the roof), short sections of roof such as overcasts, roof cavities, and intersections (with no foam on the ribs), and between buntons on one wall of a shaft. Foam on the ribs and adjoining roof presents a fire hazard. Stoppings covered with foam passing the certification tests are resistant to penetration of heat, flame, and smoke than similar stopping without foam. Flame propagation can be arrested by water sprays. Spontaneous ignition of foam can be prevented.

Jan 1, 1966

By H. V. Fairbanks

It is estimated that millions of tons of coal fines are unsaleable each year due to difficulty of drying them economically with conventional mechanical dewatering and thermal drying equipment. The difficulty is due to the fact that coal of small particle size presents a large surface area with polar groups which have a great affinity for water. In order to remove this water thermally, a high temperature is necessary which oxidizes the surface of the coal. This substantially reduces the heating value of the coal. If drying could be satisfactorily carried out at a lower temperature, much more of the heating value of the coal fines could be retained. It was conjectured that acoustic energy applied during the drying process might prove to be of value since acoustic energy has the property of producing cavitation at a liquid-solid interface when the intensity is sufficiently great. This cavitation process produces water at room temperature which can be carried away from the solid surface by a flow of relatively cool air. Hence, moisture removal is made possible at a lower temperature.

Jan 1, 1966

By John Nagy

The Bureau of Mines adapted thermal theories explaining combustion of gases to correlate parameters affecting ignition of dust dispersions. The dust dispersions were ignited in a Godbert-Greenwald furnace at atmospheric pressure. Ignition temperature and the concentrations of fuel, admixed inert powder, and atmospheric oxygen were related mathematically. Values for these parameters obtained in laboratory experiments for cornstarch agreed with theory. The developed equation permits extrapolation; the predicted upper igni-tion limits correspond with limited experimental data from laboratory and large-scale tests. Explanation of the effect of fineness of dust on ignition parameters is attempted by introducing a surface-area constant to modify the activation energy. Arguments are presented to show that the ignition process is a solid-gas phase reaction rather than an ignition of prevolatilized gases.

Jan 1, 1966