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By K-H. Frohne

This report presents a study of the Cooper sand of the Fork Run pool of Warren and McKean Counties, Pa., and a prediction of the secondary oil recovery by gasflooding the reservoir. A computer program employing a modification of the Craig, Geffen, and Morse secondary recovery calculation was used to make the gas flood performance forecast and is presented in the appendix. The Cooper sand reservoir in the Fork Run pool lies at a depth of about 1,900 feet and covers an area 1/2 mile wide by 2-1/4 miles long. Original oil in place is estimated to have been 8,266,000 STB. The primary recovery mechanism is solution gas drive, and ultimate primary recovery may reach 20 percent over a well life of 90 years. Two computer predictions were made for gas flooding the Cooper reservoir. The first was for a 25-acre pilot five-spot utilizing existing wells, but project economics were poor since only 25 percent of injection gas is utilized for pilot oil recovery. Recovery was 71,000 STB, or 22 percent of oil in place at flood initiation, but required 25,700 scf gas injected per STB of oil recovered. In the second prediction, pilot area performance was projected for the entire Fork Run pool, and economics became good. Recovery was 1,753,000 STB from 25 five-spots after the injection of only 6,400 scf per STB of oil recovered.

Jan 1, 1969

By C. W. Dwiggins

The Bureau of Mines characterized the chemical and physical properties of metallo-organic materials in petroleum to determine their effect on petroleum production and refining. The structures and physical properties of porphyrins and materials that normally contain metalloporphyrins such as crude oils and asphaltenes were investigated using elemental analysis, NMR analysis, absorption spectrometry, and small-angle X-ray scattering. Petroleum fractions greatly enriched in metalloporphyrins were obtained using asphaltene precipitation, liquid extraction, and large-scale liquid-solid chromatography. Selected fractions containing porphyrins were further purified by chromatographic methods, crystallization, and demetalation followed by chromatography. Nonporphyrin metals could not be appreciably concentrated from the bulk of the asphaltene.

Jan 1, 1969

By M. O. Serbousek

To further investigate the potential of precast concrete sets as a support medium for underground mines, the Bureau of Mines designed an eight-piece precast reinforced concrete drift set for a small opening. Twenty-two sets of three different member sizes were tested to destruction under two loading conditions. A discussion of the test results and typical failure patterns is presented.

Jan 1, 1969

By Joseph W. Town

The Bureau of Mines conducted studies related to SO2 air pollution to determine attritioning rates, SO2 sorption rates, and sulfur loads that could be obtained on commercial alkalized alumina sorbent pellets. Fluidized-bed attritioning rates ranged from 0.025 pct/hr for alkalized alumina with a crushing strength of 4 kg to 0.075 pct/hr for 0.5 kg crushing strength mate¬rial. Airlift attritioning rates ranged from 0.50 pct/hr for 3 kg crushing strength alkalized alumina to about 3 pct/hr for 0.5 kg material. Attritioning rates for the commercial alkalized alumina were comparable to those obtained for sorbent pellets prepared in the Bureau of Mines laboratory. Sorption rates were related to S02 concentration in flue gas, temperature, and presence of nitrogen oxides in the gas stream. Sorption rates at 300° C were 0.35 X 10-6 gS/gp/sec (grams sulfur per gram pellet per second) in 0.045 pct so, gas, 5.1 x 10-5 gS/gp/sec in 0.34 pct SO2 gas, and 65 X 10-5 gS/gp/sec in 10 pct SO2 gas. For the 0.34 pct S02 gas, sulfur loads of 0.10 gS/gp (the projected load for regeneration) were obtained in 47 min at 130° C and in 116 min at 300° C. The presence of either NO or NO2 in the 0.34 pet S02 gas increased the SO2 sorption rates 2 to 3 times at 300° C, but had no effect at 130° C.

Jan 1, 1969

By C. C. Shale

A semicommercia1, high-temperature electrostatic precipitator and adjunct equipment are described, and operating characteristics at 1,470° F and 80 psig are presented for both positive and negative polarity. Removal efficiency for negative corona waS about 91 to 96 percent while that for positive corona was only about 75 to 77 percent. Results are compared with those from bench-scale investigations, and equipment limitations are discussed. Theoretical aspects of the precipitation process are related to the operating characteristics.

Jan 1, 1969

By J. S. Miller

The Bureau of Mines conducted surface tests to determine the feasibility of using liquid explosives for underground rock fracturing. The effects of configuration, confinement, length, critical layer thickness, and fracture-propping sand on detonation and explosive propagation velocity of desensitized nitroglycerin were studied, using polymethyl methacrylate and glass-plate reservoirs through lengths from 3 to 12 ft, with explosive-layer thicknesses from 0.1875 to 0.0312 in and in aluminum tubes 8 ft long with diameters from 2.000 to 0.125 in. Interval and continuous detonation velocity data were obtained. Under the test conditions detonation velocity was dependent upon explosive confinement and fracture-propping sand. The detonation velocity of a confined nitroglycerin explosion in aluminum tubes can be reduced by as much as 85 percent, when the tube contains fracture-propping sand. The shape of the reservoir, whether triangular or rectangular, has little effect on the detonation velocity or explosive propagation. The critical or minimum explosive-layer thickness between glass plates, capable of supporting propagation, was 0.0312 in. The presence of a fracture-propping sand in the sheetlike layers increased the critical explosive layer thickness to 0.0625 in. In nitroglycerin-filled and nitroglycerin-sand filled tubes, the minimum tube diameters successfully tested were 0.125 in and 0.375 in, respectively.

Jan 1, 1969

By Alton B. Cook

Data are presented to show oil vaporization resulting from the passage of natural gas through a sand-packed tube saturated with synthetic reservoir oils. The Bureau of Mines performed 13 experiments, using reservoir oils synthesized with base crude oils of approximately 22°, 35°, and 45° API, at 100°, 175°, or 250° F and 1,100, 2,600, or 4,100 psia. It has been determined that the amount of vaporization is significant if proper conditions exist. These experiments show that oil vaporization depends on pressure, temperature, volatility of the oil, and amount of gas cycled. Increases in each of these conditions increase the volume of oil vaporized.

Jan 1, 1969

By John Nagy

The Bureau of Mines examined explosion development in a closed spherical vessel, mathematically correlating flame travel, pressure, and time with parameters defining the reaction. The model assumes that burnt and unburnt zones are separated by a thin, radially moving flame front. Isothermal and adiabatic systems are considered. Correlation with gas and dust explosion data is better for the adiabatic system, but the isothermal development is simpler and in reasonably good agreement. Interpretation of the explosion phenomena is facilitated by expressing the rate of mole change in the flame front in terms of elementary parameters. This expression is developed by examining the components of spatial-flame velocity.

Jan 1, 1969

By L. B. Pankratz

The Bureau of Mines determined low-and high-temperature thermodynamic properties for anhydrous ferric sulfate and anhydrous indium sulfate. Low-temperature heat capacities were measured between 50° and 298° K, and enthalpy increments above 298° K were determined. The high-temperature measurements of Fe2(S04)3 extended to 900° K and those of In2(S04)3 to about 1,000° K. A minor transition was found for Fe2(S04)3 at 800° K, with a heat of transition of 540 cal/mole. Tabulations were made of the low-temperature heat capacities and the high-temperature enthalpy and entropy increments. The 298° K entropies derived from the low-temperature measurements were 67.6±0.S ca1/deg mole for ferric sulfate and 72.2±O.5 cal/deg mole for indium sulfate. High-temperature enthalpy increments were also given in equation form.

Jan 1, 1969

By Charles C. Boley

The Bureau of Mines dried and carbonized two wood wastes, one softwood (redwood) and one hardwood (oak), using continuous, vertical entrainment techniques previously developed for use with coal. It was demonstrated that these techniques are readily applicable to wood waste and that appreciable changes in the yields of carbonization products can be obtained by varying operating conditions. A limited amount of experimental work was done on briquetting the char-coals. Firm briquets were formed with oak charcoal, although greater quantities of starch binder than used commercially for kiln-produced charcoal were required. Redwood charcoal did not briquet successfully under the test conditions employed.

Jan 1, 1969

By Charles C. Boley

The Bureau of Mines dried and carbonized two wood wastes, one softwood (redwood) and one hardwood (oak), using continuous, vertical entrainment techniques previously developed for use with coal. It was demonstrated that these techniques are readily applicable to wood waste and that appreciable changes in the yields of carbonization products can be obtained by varying operating conditions. A limited amount of experimental work was done on briquetting the charcoals. Firm briquets were formed with oak charcoal, although greater quantities of starch binder than used commercially for kiln-produced charcoal were required. Redwood charcoal did not briquet successfully under the test conditions employed.

Jan 1, 1969

By R. S. Fowkes

The Bureau of Mines constructed a fully automated pilot plant facility to study the hydraulic transportation of solids through a lock hopper feeder system. An equation for the energy requirements to transport coarse solids hydraulically proved applicable to this system. Optimum velocities were obtained for limestone, mine refuse, and bituminous coal. The experimental data, calculations, and graphs show the effect of velocity, specific gravity, and solids concentration on head loss and power requirements. Other data were obtained and evaluated to determine the effect of particle size on head loss. Results also are given for (a) tests using friction reducing polymers; (b) tests using seven test sections of steel alloy pipe to determine their wear characteristics; (c) tests to determine spatial segregation of moving particles; and (d) tests to determine the effect of shape, size, and specific gravity on particle velocity in a horizontal pipeline. The lock hopper feeder system was found practical for continuous hydraulic transportation of the material types and size ranges tested.

Jan 1, 1969

By J. L. Konchesky

The Bureau of Mines investigated the main reactions of coal gasification by steam. Coal (minus 70 mesh)-water slurry was fed into a laboratory-scale tube-coil gasifier to show the effects of residence time (0.6 to 1.1 sec), steam-coal ratio (2 to 11 lb/lb), and temperature (1,600° to 1,900° F), at about 1-1/2 atm. Devolatilization was very rapid: about 70 pet of the coal's volatile matter evolved within 0.6 sec at about 1,600° F; temperature increase released more volatile matter until about 95 pct was driven off at 1,900° F. Devolatilization was not increased by raising steam concentrations and was only slightly increased by extending residence time. Below 1,600° F, there was no evidence of the steam-carbon reaction, but at 1,900° F more than 80 pct of the coal's fixed carbon was converted to gas; the conversion was increased Significantly by increased residence time and steam concentration. The water-gas shift reaction occurred simultaneously with devolatilization, and the steam-carbon reaction, approaching equilibrium with increased residence time and temperature and decreased steam concentration.

Jan 1, 1969

By M. M. Tilman

In a Bureau of Mines investigation to develop lead alloys with improved tensile strength and creep resistance, lead-base alloys containing cadmium and antimony in nominal 1-to-1 atomic ratios were melted in air, cast, and rolled into sheet to 90 percent reduction at temperatures varying from room temperature to 175° C. Tensile testing at room temperature and stress-rupture testing at 900±3° F were conducted on the as-rolled alloys. The best tensile properties were observed in an alloy of Pb-4.2 wt pct Cd-4.5 wt pct Sb which exhibited an average tensile strength of 7,270 psi with 36 percent elongation in 2 inches. An alloy of Pb-5.5 wt pct Cd-6.0 wt pct Sb had 100-hour stress-rupture values of approximately 2,100 psi and 1,000-hour values of approximately 1,700 psi.

Jan 1, 1969

By John Ward Smith

An analytical method developed by the Bureau of Mines to determine dawsonite, nahcolite, and nondawsonite alumina (called excess alumina) extractable from Green River Formation oil shales is presented. The method requires water extraction of nahcolite followed by HCI-extraction of dawsonite and an unidentified mineral yielding excess alumina from the water-leached residue. Instrumental determination of sodium in the water extract and sodium and aluminum in the HCI extract measures the sample's content of the minerals. Detailed evaluation shows the method to be adequately specific, precise, and reproducible and free from uncorrectable interferences. The method's results define precisely the production of sodium carbonates and alumina possible from a sample of oil shale and the interval it represents. Shale-oil yields, nahcolite contents, and yields of extractable alumina determined on 83 samples representing an 821-foot section of dawsonite-nahcolite-bearing shale from .Colorado Corehole No.3, drilled in the north part of Colorado's Piceance Creek Basin, are presented. These samples resulted in nahcolite contents to 53.3 percent, oil yields to 48.3 gallons per ton, and alumina yields to 5.80 percent. Use of these data to evaluate the production potential of a section of the formation are suggested.

Jan 1, 1969

By Ted C. Briggs

The Bureau of Mines is evaluating the thermodynamic properties of helium and helium-containing mixtures. Twenty-two compressibility runs were made with helium at 0° C and pressures to 800 atmospheres using a Burnett-type apparatus. Data from the 22 runs were treated simultaneously and as separate runs while different functional forms and weighting factors were used. A fourth-degree-polynomial equation in the pressure gives a statistically satisfactory representation of the compressibility factor when the data are treated simultaneously and a weighting factor of Pr-3/4 is used. The second virial coefficient of helium at 0° C from this investigation is 11.997±0.015 cm3 mole-1. The stated uncertainty is the random error standard deviation. Compressibility factors determined by this investigation are precise to better than 0.01 percent and are believed to be accurate to better than 0.02 percent.

Jan 1, 1969

By Richard Havens

Acidic and basic uranium leach plant residues located on the Navajo Indian Reservation, Tuba City, Ariz., were successfully stabilized against wind erosion using a relatively low-cost chemical method. An elastomeric polymer chemical was applied to the dike areas and a calcium magnesium lignosulfonate to the beach areas of three tailings ponds. The water-soluble chemicals were applied with an automated sprinkling system. The stabilization cost was $335 per acre for the 34.5-acre tract.

Jan 1, 1969

By Danton L. Paulson

Elevated temperature electrical resistivity measurements were made by the Bureau of Mines on arc-melted, spin-cast, and hot-pressed columbium carbide¬carbon (CbC-C) and zirconium carbide-carbon (ZrC-C) materials up to 2,000° C. The CbC-C materials displayed electrical resistivity values ranging from 35.20 microhm cm at 23° C for hot-pressed material containing 12 wt pct carbon to 242.64 microhm cm at 1,622° C for arc-cast material containing 17.0 wt pct carbon. Electrical resistivity values ranged from 29 microhm cm at 20° C for arc-cast ZrC-C containing 16 wt pct carbon to 279 microhm cm at 1,951° C for hot-pressed ZrC-C containing 21 wt pct carbon. Data from a previous report were included to establish comparison between the electrical resistivities of the CbC-C, ZrC-C, and HfC-C systems.

Jan 1, 1969

By M. M. Fine

Research on the solid-fuel reduction of Knob Lake iron or was conducted to upgrade lean and high-grade ores and recover metallized products suitable for ironmaking or steelmaking. The program included bench-scale tests plus a number of continuous campaigns in a 34-inch by 36-foot rotary kiln. In the laboratory, metallizations in excess of 90 percent were achieved by reduction of crushed ore with lignite at 950° C. Subsequent grinding (to minus 200 mesh) and wet magnetic separation yielded concentrates analyzing less than 3.0 percent SiO2 and more than 90 percent Fe. Virtually complete recovery of the iron occurred. During early continuous tests the crushed ore created a serious ringing in the kiln which was solved by balling the fines with bentonite. Unfortunately, at this temperature (950° C) the bentonite militates against the concentratability of the metallized product. For example, a run on direct-shipping ore produced concentrates of 89.5 percent Fe and 4.5 percent SiO2. At 500° C the adverse effect of bentonite disappeared and concentrates of 88.4 Fe and only 2.5 percent SiO2 resulted. However, with comparable feed r Los, the metallization dropped to 73 percent.

Jan 1, 1969

By B. H. Eccleston

The Bureau of Mines, in cooperation with the American Petroleum Institute, studied the effect of fuel volatility and front-end fuel composition on the amount and photochemical reactivity of automobile exhaust and fuel-system evaporative emissions. The study involved six gasolines--the base fuel, three fuels of varied volatility, and two fuels differing from the base and from each other in front-end olefin content. Data were obtained from 16 vehicles operated on a chassis dynamometer using a speed-load-time cycle that approximated a typical urban trip. Tests were made at ambient temperatures of 20°; 45°, 70°, and 95° F, using a climate-controlled dynamometer room. The amount of hydrocarbon emission and its probable photochemical effect, a potential contribution to pollution, is expressed as weight (reactivity equivalent) of a moderately reactive material, ethylene. Emissions of oxides of nitrogen, car-bon monoxide, and aldehydes were also observed. Results showed that reduction of volatility from currently typical levels serves to reduce both the amount and the reactivity equivalent of evaporative losses with a slight penalty by way of higher exhaust emissions. Alternatively, reducing the amount of light (low boiling) olefin in the fuel had no effect on the amount of hydrocarbon pollutant but did significantly reduce the reactivity equivalent of the emissions. Neither volatility change nor chemical changes to the fuel significantly affected the nonhydrocarbon emissions.

Jan 1, 1970