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By K. H. Coats

In tnany oil and gas fields, significant investments are required in piping networks for collection, injection and disposal of various fluids. This paper treats the problem of optimally locating the trunkline(s) for a given systet to nlinimize both the total length of piping connecting the individual wells or lease batteries to the trunkline and the length of the latter. Single and multiple trunklines, varying line sizes, and grouping of wells are considered. Some attention is paid to the case of a curved trunkline. A field case is treated and conclusions are that the problem of locating a single trunkline is relatively straightforward while the location of multiple trunklines requires further research. INTRODUCTION la many oil and gas fields, significant investments are required in piping networks for collection, injection and disposal of various fluids. A single field may concurrently require piping systems for gathering of oil, gathering of gas, injection of water or gas and disposal of salt water. Two problems arise in the consideration of any one of these networks. The first involves the sizing of the various segments of the network to minimize piping and compression costs. The second problem, treated herein, is that of optimally locating the trunkline(s) for a given piping system to minimize the total length of pipe connecting the individual wells or lease batteries to the trunkline. This minimization problem may arise in field automation if it involves replacement of individual lease batteries by a central field battery which will require trunklines and connecting pipelines to individual wells. The problem also arises in connecting a gas pipeline through a subsidiary trunkline to wells in a gas storage field. The first analysis given below treats the case of a single trunkline and of separate connecting lines for all field units.* The analysis is then extended to consider multiple trunklines and common connecting lines for groups of field units. Varying sizes, and therefore costs, of the connecting lines are taken into account. A simplified development is given to illustrate the manner in which line sizing calculations may be integrated with the line placement problem. This study is primarily directed toward the placement of straight trunklines, although for certain field shapes or well distributions curved trunk-lines might be preferable. Some mathematical consideration is therefore given to the placement of a curved trunk-line in a field. The determination of optimal locations for two or more trunklines involves some difficulties which are discussed below. The need for further research in this area is emphasized. The problem of a single trunkline is solved in relation to an actual oil field. The problem of optimally locating two trunklines in the same field is also treated and the results are compared to the single-trunkline case. All calculations reported were performed on an IBM 7072 digital compker. The importance of right-of-way, roads and terrain in locating trunklines and connecting lines is realized. The present analysis is advanced on the premise that in planning piping networks one should start with the optimal conditions whenever possible and proceed therefrom.

By David B. Reger

The expansion of the previously discovered gas pools and an intensified search for additional pools in the Oriskany and deeper sands were the principal petroleum activities in West Virginia during 1941. One small oil pool was discovered and another was considerably extended. One small gas pool was discovered, several isolated well discoveries were expanded into definite pools, and various recognized pools were substantially increased. The proved oil territory of the state was increased about 600 acres and the proved gas territory about 45,000 acres. The new discoveries of oil did not equal withdrawals but gas reserves added were greater than gas withdrawals. Oil activity, as in the past several years, was slight because of unfavorable crude prices. Most operators prefer to leave oil in the ground rather than to drill for it without a better return. Gas activity increased greatly because of better demand, even though the price of gas did not improve. The account of operations, as gathered from trade journals and other reporting services, shows that 838 new wells were drilled, resulting in 114 new oil wells with 2606 bbl. of daily new production; 558 new gas wells with 949,226,000 cu. ft. of daily open flow; and 166 dry holes. Also, 86 old wells were drilled to deeper sands with 9 bbl. and 56,030,000 cu. ft. of added production. On the new wells the oil average was 22.86 bbl. per well per day; and the gas average was 1,701,000 cu. ft. per well per day. On new wells the ratio of dry holes to completions was 13.61 per cent. On deeper drilling to other sands the ratio of failures was 15.12 per cent. From an exploratory standpoint one strictly new oil pool (Higginbotham Run) was opened in Kanawha County and one strictly new gas pool (Lost Run) in Taylor County. One entirely isolated wildcat gave commercial Oriskany-sand gas production and may open a pool. Various other wildcats greatly extended the boundaries of known Oriskany-sand gas pools and various others may have opened new pools in the shallow sands. On the other hand, various Oriskany tests in Harrison, Monongalia, Roane and Wood Counties were dry and all five tests to the White Clinton sand (Sil.) in Boone, Harrison, Kanawha and Wood Counties failed to find commercial production. The principal oil wells completed, by counties, were: Calhoun, 24; Clay, 7; Gilmer, 6; Hancock, 9; Kanawha, 9; Pleasants, 10; and Ritchie, 14. Production for the year was estimated by the Oil Weekly as 3,421,000 bbl., compared with U. S. Bureau of Mines final figures of 3,444,000 bbl. in 1940. The leading counties in gas-well completions were: Boone, 32; Braxton, 19; Cabell, 16; Calhoun, 46; Clay, 20; Gilmer, 37; Jackson, 94; Kanawha, 82; Lincoln, 17; Putnam, 46; Ritchie, 33; Upshur, 20; and Wayne, 33. Production for the year is estimated by the author as 210,000,000,000 cu. ft., as compared to the U. S. Bureau of Mines' final figures of 188,751,000,000 cu. ft.* in 1940.

Jan 1, 1942

By David B. Reger

The expansion of the previously discovered gas pools and an intensified search for additional pools in the Oriskany and deeper sands were the principal petroleum activities in West Virginia during 1941. One small oil pool was discovered and another was considerably extended. One small gas pool was discovered, several isolated well discoveries were expanded into definite pools, and various recognized pools were substantially increased. The proved oil territory of the state was increased about 600 acres and the proved gas territory about 45,000 acres. The new discoveries of oil did not equal withdrawals but gas reserves added were greater than gas withdrawals. Oil activity, as in the past several years, was slight because of unfavorable crude prices. Most operators prefer to leave oil in the ground rather than to drill for it without a better return. Gas activity increased greatly because of better demand, even though the price of gas did not improve. The account of operations, as gathered from trade journals and other reporting services, shows that 838 new wells were drilled, resulting in 114 new oil wells with 2606 bbl. of daily new production; 558 new gas wells with 949,226,000 cu. ft. of daily open flow; and 166 dry holes. Also, 86 old wells were drilled to deeper sands with 9 bbl. and 56,030,000 cu. ft. of added production. On the new wells the oil average was 22.86 bbl. per well per day; and the gas average was 1,701,000 cu. ft. per well per day. On new wells the ratio of dry holes to completions was 13.61 per cent. On deeper drilling to other sands the ratio of failures was 15.12 per cent. From an exploratory standpoint one strictly new oil pool (Higginbotham Run) was opened in Kanawha County and one strictly new gas pool (Lost Run) in Taylor County. One entirely isolated wildcat gave commercial Oriskany-sand gas production and may open a pool. Various other wildcats greatly extended the boundaries of known Oriskany-sand gas pools and various others may have opened new pools in the shallow sands. On the other hand, various Oriskany tests in Harrison, Monongalia, Roane and Wood Counties were dry and all five tests to the White Clinton sand (Sil.) in Boone, Harrison, Kanawha and Wood Counties failed to find commercial production. The principal oil wells completed, by counties, were: Calhoun, 24; Clay, 7; Gilmer, 6; Hancock, 9; Kanawha, 9; Pleasants, 10; and Ritchie, 14. Production for the year was estimated by the Oil Weekly as 3,421,000 bbl., compared with U. S. Bureau of Mines final figures of 3,444,000 bbl. in 1940. The leading counties in gas-well completions were: Boone, 32; Braxton, 19; Cabell, 16; Calhoun, 46; Clay, 20; Gilmer, 37; Jackson, 94; Kanawha, 82; Lincoln, 17; Putnam, 46; Ritchie, 33; Upshur, 20; and Wayne, 33. Production for the year is estimated by the author as 210,000,000,000 cu. ft., as compared to the U. S. Bureau of Mines' final figures of 188,751,000,000 cu. ft.* in 1940.

Jan 1, 1942

By Nicholas J. Grant, Klaus M. Zwilsky

EVER since the unusual high temperature creep resistance and structure stability of SAP (Sintered Aluminum Powder) and similar aluminum-alumina alloys were reported,'," there has been a need to determine whether other metal-metal oxide (or other hard stable particle) alloys, not so ideal as the Al-Al 2 O 3 system, would show similar high temperature strength and stability. Of the many possible methods of obtaining a metal-metal oxide alloy,a one that offers many practical and theoretical advantages is the simple mechanical blending of metal powders with hard stable particles, followed by pressing, sintering, and hot extruding. With this purpose in mind copper powder and silica and alumina were selected for experimentation because these materials are readily available, cheap, reliable, and lend themseives te the simplest processing and testing. Starting Materials—Two sizes of electrolytically deposited copper powders were used, a —200 mesh powder referred to as A powder in this investigation and a —325 mesh powder referred to as C powder. Silica was added in the form of pure Potter's flint from which a —10µ fraction had been separated. Alumina of the a variety was used in two size ranges. The first was a —10µ fraction separated from a coarser aggregate, the second a commercial product of 0.3µ average diam manufactured by Linde Air Products. Preparation of Powders—Five-hundred gram batches of A copper with 1, 3, and 10 volume pct of each of the three oxides mentioned above were prepared, as well as C copper containing 1, 3, and 10 volume pct of —lop silica. Powders were weighed out carefully and blended by ball milling in air for 24 hr. Since this treatment resulted in surface oxidation of the copper, the charge was hydrogen reduced at 260°C for 5 hr. The next step consisted of hydrostatically compacting the powder into a shape suitable for the required hot working. For this purpose a slug about 11/2 in. in diam and 31/2 in. in length was produced by placing the mixed powders into a rubber sleeve, holding in a perforated steel canister, and rubber stoppering at the ends; the assembly was then subjected to a hydrostatic pressure of 50,000 psi. The air was evacuated from the assembly prior to pressing in order to prevent

Jan 1, 1958

By G. S. Hume

Petroleum is produced in Canada in the provinces of New Brunswick, Ontario and Alberta and in the Northwest Territories. The total production, however, is relatively small in comparison with the consumption, the value of imports exceeding 40 million dollars a year. Production figures are given in Tables 1 and 2. In Turner Valley, still the largest producing gas and oil field in Canada, five wells were completed during the year. The largest of these

Jan 1, 1936

By G. S. Hume

Petroleum is produced in Canada in the provinces of New Brunswick, Ontario and Alberta and in the Northwest Territories. The total production, however, is relatively small in comparison with the consumption, the value of imports exceeding 40 million dollars a year. Production figures are given in Tables 1 and 2. In Turner Valley, still the largest producing gas and oil field in Canada, five wells were completed during the year. The largest of these

Jan 1, 1936

By P. R. Kneitz, G. Yoshikado, D. Zayakov

The design and analysis of a circular, domed powerhouse for Pacific Gas and Electric (PG&E) Company's Kerckhoff 2 Project is described. Exploration, geologic stress determinations, mechanical properties, reinforcement and instrumentation are addressed briefly. The analyses of the circular, domed cavern and the comparison of predicted and field deformations are presented in somewhat more detail. The behavior of the completed powerhouse cavern has been found to be substantially as predicted by the analysis.

Jan 1, 1982

By William A. Mitchell

AN X-ray diffraction pattern for "calcined cold precipitated ferric oxide" is reproduced diagrammatically along with data for other iron oxides by R. C. Mackenzie.1 This pattern, which shows spacings higher than those for any other form of iron oxide, was obtained from material prepared and photographed at several different times over a period of weeks, but later attempts to reproduce the results were unsuccessful the pattern of hematite being obtained every time.2

Jan 9, 1953

By James A. Beck

Phosphorus is essential to all life processes and therefore to the existence of man. In this role, there are no substitutes for phosphorus. In a commercial sense, phosphorus and its compounds are important to our entire economy, both in agricultural and in nonagricultural applications. The world's phosphate requirements are met by mining phosphate rock. Two general types of phosphate ore deposits are commercially important-igneous and sedimentary. Igneous deposits generally are more difficult and more expensive to mine than sedimentary deposits and are of importance mainly in the USSR, North Vietnam, and South Africa. Approximately 15% of current world production comes from these deposits. Over 80% of world production is from the pellet sedimentary deposits of Florida, North Africa, and elsewhere. Guano, the second type of sedimentary deposit, is produced in South America but is declining in world importance. Production Production of phosphate rock was reported in 31 countries during 1972. However, about 80% of world output is produced in three countries: the United States, the USSR, and Morocco (Table 15.2A.1). Throughout the past 20 years, between 75% and 80% of world output has been produced by these three leading countries. Between 1948 and 1972 world production increased at an average rate of 10% per year, from 21.5 to 103.9 million tons. Growth was quite steady at 6% per year through 1963, but in the 5 years from 1963 to 1968 production increased 11 1/2% per year. Since 1968 production has increased about 91/2 % annually. Since 1948 several new phosphate mining ventures have been developed in Senegal, Togo, Israel, and North Vietnam. In the same period, only one important phosphate deposit, on Makatea Island, has been mined out and closed. A number of other phosphate mining ventures are in various stages of planning and development. The most important new venture in phosphate mining is in the Spanish Sahara. New mining capacity is expected also in Syria, and serious investigation is in progress in Peru, India, Turkey, and Australia. Major expansion of existing operations is expected in Morocco, Russia, Tunisia, Israel, and Jordan. Consumption Historical data on world consumption of phosphate rock are not available in detail, but world consumption of phosphate has closely paralleled world production in the past two decades. The United States is the world's largest user of phosphate rock, accounting for 30%

Jan 1, 1976

By Roscoe C. Clark

In October 1945. R. F. Farris. in an AIME paper entitled Method For Drtermining Minimum Waiting OIL Cenzent Time, presented a method for caiculating the minimum WOC* time required in oil well cementing operations. Briefly. this method consisted of shutting in a well. after the cement had been placed and noting the time required fur the wellhead pressure to reach a. maximum. This time was then multiplied by a factor of 1.5 to determine when the cement had reached sufficient strength to support the weight of the casing. As a result of this work, a number of areas have reduced their WOC time ~Wuirements with the subsequent saving of considerable rig time. The tests conducted by Farris were, for the most part, conducted under cementing temperatures in excess of 70°F. This was done because in the overwhelming majority of cases. cementing temperatures are in excess of 70°F (only in tile northern part of the country. primarily in the Rocky Mountain ares. in cementing surface casing are temperatures below 70° F. encountered, and such temperatures occur only during the winter months). The Stano-lind Research Laboratory since that time has performed a number of tests both in the laboratory and in the field to evaluate this WOC factor when cemeriting temperatures are lower than 70°F. The results of these tests indicated the need for greater WOC time in areas affeaed by abnormally low cementing temperatures. These tests indi.cated that a woc factor of 2 (Time from start to mix cement to maximum wellhead pressure x 2 = Time to drill plug) will allow sufficient time for the cement to develop adequate strength. A field test under abnormally low cementing temperatures (surface temyerature 35°F., mud discharge temperature <70°F. and cementing depth 500 ft.) in the Rangely Field, "* using the WOC factor of 2, indicated the time to drill the plug as 45 hours. Well conditions preventing getting back into the well until a 48-hour WOC time had elapsed. At this time, the plug drilled firm to hard indicating that the cement had reached its final set. It is contemplated that during next winter additional field tests will be performed to further check the results of the laboratory and field tests conducted to date,

Jan 1, 1949

By Roscoe C. Clark

In October 1945. R. F. Farris. in an AIME paper entitled Method For Drtermining Minimum Waiting OIL Cenzent Time, presented a method for caiculating the minimum WOC* time required in oil well cementing operations. Briefly. this method consisted of shutting in a well. after the cement had been placed and noting the time required fur the wellhead pressure to reach a. maximum. This time was then multiplied by a factor of 1.5 to determine when the cement had reached sufficient strength to support the weight of the casing. As a result of this work, a number of areas have reduced their WOC time ~Wuirements with the subsequent saving of considerable rig time. The tests conducted by Farris were, for the most part, conducted under cementing temperatures in excess of 70°F. This was done because in the overwhelming majority of cases. cementing temperatures are in excess of 70°F (only in tile northern part of the country. primarily in the Rocky Mountain ares. in cementing surface casing are temperatures below 70° F. encountered, and such temperatures occur only during the winter months). The Stano-lind Research Laboratory since that time has performed a number of tests both in the laboratory and in the field to evaluate this WOC factor when cemeriting temperatures are lower than 70°F. The results of these tests indicated the need for greater WOC time in areas affeaed by abnormally low cementing temperatures. These tests indi.cated that a woc factor of 2 (Time from start to mix cement to maximum wellhead pressure x 2 = Time to drill plug) will allow sufficient time for the cement to develop adequate strength. A field test under abnormally low cementing temperatures (surface temyerature 35°F., mud discharge temperature <70°F. and cementing depth 500 ft.) in the Rangely Field, "* using the WOC factor of 2, indicated the time to drill the plug as 45 hours. Well conditions preventing getting back into the well until a 48-hour WOC time had elapsed. At this time, the plug drilled firm to hard indicating that the cement had reached its final set. It is contemplated that during next winter additional field tests will be performed to further check the results of the laboratory and field tests conducted to date,

Jan 1, 1949

LIMA (PERU) Established May, 1952 (Official year begins in June) Luncheon meetings third Wednesday monthly Ernesto A Baertl, Chairman Arthur C Hall, Chairman-elect Raymond R Beard, 1st Vice-Chairman Edgardo Portaro, 2nd Vice-Chairman Walter E King, Secretary-Treasurer Av Santa Cruz 331 San Isidro, Lima, Peru Alberto E Brazzini, Asst Treasurer Daniel M Rodriguez, Asst Secretary Robert P Koenig, &apos;56, Section Delegate Arthur C Hall, Alternate Section Delegate

Jan 1, 1955

By Claude H. P. Lupis, John F. Elliott

WAGNERL described the thermodynamic behavior of a metallic solution consisting of the solute components 2, 3,... at very dilute concentrations in the solvent, 1, in terms of the excess partial molar free energy, or alternatively the logarithm of the activity coefficient. In the Taylor expansion of FiE, by neglecting the second- and higher-order differential terms, he obtained the excess partial molar free energy as a linear function of the composition:

Jan 1, 1965

Buffalo Society of Natural Sciences, Buffalo Museum of Science, Humboldt Park, Buffalo, N Y. Of the many scientific bulletins issued by the Society only one of those now available is of particular interest in this directory. Vol 7 (1901), Bulletin 1, Guide to the geology and paleontology of Niagara Falls and vicinity, by A. W. Grabau, $1 unbound or $2 bound. The bulletins are distributed through the Research Librarian at the above address

Jan 1, 1933

[NUMERICAL CODE TO MAPS (Region Listed in Roman Numerals after Each Petroleum Section) 1 Alaska 2 Arizona 3 Black Hills 4 Boston 5 Carlsbad Potash 6 Central Appalachia 7 Chicago 8 Cleveland 9 Colorado 10 Columbia 11 Connecticut 12 Delta (VIII) 13 Detroit 14 East Texas (VI) 15 El Paso 16 Gulf Coast (VII) 17 Kansas (IX) 18 Lehigh Volley 19 Mid-Continent (IX) 20 Minnesota 21 Montana 22 Nevada 23 New York]

Jan 1, 1961

By M. Sheffield

This paper presents a technique lor predicting the flow of oil, gas and water through a petroleum reservoir. Gravitational, viscous arid capillary lorces are considered, and all fluids are considered to be slightly compressible. Some theoretical work concerning the fluid flow in one-, two- and three-space dimensions is given along with example performance predictions in one- and two-space dimensions. INTRODUCTION Since the introduction of high speed computing equipment, one of the goals of reservoir engineering research has been to develop more accurate methods of describing fluid movement through underground reservoirs. Various mathematical methods have been developed or used by reservoir engineers to predict reservoir performance, 193-5,7,8 The work reported in this paper extends previously published work on three-phase fluid flow (1) by including a rigorous treatment of capillary forces and (2) by showing certain theoretical mathematical results proving that these equations can be approximated by certain numerical techniques and that a unique solution exists. DISCUSSION The method of predicting three-phase compressible fluid flow. in a reservoir can be summarized briefly by the following steps. 1. The reservoir, or a section of a reservoir, is characterized by a series of mesh points with varying rock and fluid properties simulated at each mesh point. 2. Three partial differential equations are written to describe the movement at any point in the reservoir of each of the three compressible fluids. All forces influencing movement are considered in the equations. 3. At each mesh point, the partial differential equations are replaced by a system of analogous difference equations. 4. A numerical technique is used to solve the resulting system of difference equations. Capillary forces have been included in two-phase flow calculations.1,4,8 The literature, however, does not contain examples of prediction techniques for three-phase flow that include capillary forces. Where capillary forces are considered, each of the three partial differential equations previously discussed has a different dependent variable, namely pressure in one of the three fluid phases. Therefore, three difference equations must be solved at each point in the reservoir. Where large systems of equations must be solved simultaneously, an engineer might question whether a unique solution to this system of equations actually exists and, if so, what numerical techniques may be used to obtain a good approximation to the solution. It is shown in the Appendix that a unique solution to the three-phase flow problem, as formulated, always exists. It is also shown that several methods may be used to obtain a good approximation to the solution. The partial differential equations and differenceequations used are shown in the Appendix. Matrix notation has been used in developing the mathematical results. Two sample problems were solved on a CDC 1604. They illustrate the type of problems that can be solved using a three-phase prediction technique. SAMPLE ONE-DIMENSIONAL RESERVOIR PERFORMANCE PREDICTION A hypothetical reservoir was studied to provide an example of a one-dimensional problem that can be solved. Of the several techniques available, the direct method of solution as shown in the Appendix was used. The reservoir section studied was a truncated, wedge-shaped section, 2,400 ft long, with a 6&apos; dip. (A schematic is shown in Fig. 1.) This section was represented by 49 mesh points, uniformly spaced at 50-ft intervals. The upper end of the wedge was 2 ft wide, and the lower end was 6 ft wide. The section

Jan 1, 1970

By J. W. Rutter, K. T. Aust

The temperature dependence of the rate of grain boundary migration was measured in bicrystals of zone-refined lead containing from 20 to less than 1 ppm by wezght of tin. The apparent activation energy in the temperature range from 320" to 200oC is markedly dependent upon the solute tin concentration and upon the orientation relationship of the grains adjacent to the grain boundavy. The quantitative experimental observat~ons are compared with the predictions of various theories of grain boundary migration. In previous work.&apos;?&apos; the mobility of individual grain boundaries was studied as a function of impurity concentration and type of boundary. Grain boundary migration occurred at the expense of dislocation arrays which were introduced into the specimen during solidification. Boundary mobility in zone-refined lead at 300°C was markedly decreased by small additions of tin. 0.004 wt pct being sufficient to decrease the rate of grain boundary migration by a factor of 1000. The mobility of grain boundaries having polar orientation relationships near 38 and 22 deg about <Ill>, and 28 deg about <100>, was much less sensitive to tin concentration in the range studied. As a result, these boundaries have relatively high mobilities. The present paper is a continuation of the above study. Data are now presented on the temperature dependence of the motion of individual grain boundaries in zone-refined lead as a function of solute tin concentration and orientation relationship of adjacent grains at the grain boundary. The experimental observations are compared with the predictions of a number of theories of grain boundary migration3-8 which, prior to the present experimental investigation, could not be critically evaluated. EXPERIMENTAL PROCEDURE The striation or lineage structure of melt-grown single crystals of zone-refined lead, containing various additions of tin, was utilized to provide a driving force for grain boundary migration, as previously described.1,2 Each grain boundary under study separated the striated single crystal from another grain which was introduced by localized plastic deformation and recrystallization of a small region of the sample. The speed of migration of grain boundaries in dilute alloys of tin in zone-refined lead was investigated as a function of 1) tin concentration from < 0.0001 to 0.002 wt pct, 2) temperature in the range of 200" to 320°C, and 3) orientation relationship of the adjacent grains at the grain boundary. The substructure driving energy available for grain boundary migration was estimated to be about 4000 ergs per cu cm, within a factor of two, from specimen to specimen.&apos; The specimen dimensions, and growth and alloying procedures for the preparation of striated single crystals of lead of known tin composition, were as described previously.&apos; Each bicrystal was carefully wrapped in aluminum foil, and annealed in a well-stirred salt bath consisting of 50 pct NaNO2 and 50 pct KNO3, for known periods of time at a series of constant temperatures (*2°C). The grain boundary positions, before and after each anneal, were determined by etching lightly in a solution of 5 pct nitric acid in methyl alcohol, in order to follow the motion of the boundary and determine its rate of migration. Thus, the rate of motion of the grain boundary in a single specimen was measured at various temperatures. The above procedure was carried out for each grain boundary in seventeen different bicrystal specimens.

Jan 1, 1960

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k&apos; where k&apos; is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

By Robert L. Dean, Michael Hoch, Samuel M. Wolosin, Chung K. Hwu

The general shape of the 1450°C isotherm of the Ti-TiO-ZrO2-Zr region was evaluated from the surrounding binary phase diagrams and from thermo-dynamic data on the metal-oxygen binaries. The phase boundaries were accurately determined using X-ray and metallographic techniques. At 1450°C the system shows a large bcc ß field, which extends from the two metal-oxygen binary systems as a Gaussian error function, and is stable up to 30 at. pct 0 when Ti and Zr are present in equal amounts. At higher O Concentrations, the ß field is in equilibrium with t-ZrO . The following four regions, with three solid phases, are present: two a ß t-ZrO,, a TW t-ZrO,, and TiO t-ZrO2 c-ZrO2. On cooling the ß phase transforms into the a phase, going through the w transition phase. The isotherm at 1500°C for the region TiO-TiO,-ZrO, was obtained by using X-ray diffraction. At 1500°C a large c-ZrOz region is present as well as a large two-phase field, Ti0 c-ZrO,. The following regions, with three solid phases in equilibrium, were found These regions are relatively small. The solidus and liquidus relationships were determined by observing samples suspended in a tungsten crucible by means of a fine tungsten wire and heated in vacuum. Eleven univariant points were found. C-ZrO, decomposes through a peritectic reaction into liquid t-ZrO2. The activities of Ti and TiO in the TiO t-ZrOz and in the two a ß t-ZrO regions were measured using the Knudsen effusion method. In the a TiO t-ZrO, region the activities of Ti and Ti are the same, as in the a — Ti TiO binary. In the two a t-ZrO, regions, the Ti activity is high and the Ti0 activity very low, although all phases present contain at least 30 at. pct 0. This indicates a short-range order in the solid phases, Zr atoms being preferentially surrounded by 0. 1 HE system Ti-Zr-0 is of interest because of the wide ranges of solid solubility exhibited by the boundary systems; as titanium and zirconium both belong to the same group of the periodic table, large single-phase regions should occur within the system, with a great variation of properties (as the composition changes within the single-phase region). Furthermore, the possibility of modifying ZrO, to make it a more usable refractory by the addition of other metals makes this system also of interest. Because of the high affinity of titanium and zirconium for oxygen, the oxygen partial pressure is very low at all compositions; thus, there exists a ternary metal-metal-oxygen system in which the oxygen pressure is not an important variable, so long as it is low enough. When a sample is heated in vacuum to a temperature high enough for vaporization to occur, the vapor phase will consist of metal and metal-oxide gas, the oxygen concentration being very low. The phase relationships in the surrounding binary systems have already been reported in the literature; therefore, the study of the ternary diagram

Jan 1, 1962

By B. K. Larkin, H. R. Bailey

One of the most complicated and potentially one of the most promising secondary recovery methods is that of underground combustion. A number of field tests1,2,3 have been performed recently, apparently indicating that the underground combustion process is technically feasible. Relatively little has been published concerning laboratory or theoretical investigations of the underground combustion process. A few results of laboratory tube runs have been published4,5 and these data are valuable in understanding the process. The tube run data also emphasize the complexity of the thermal recovery process. Under various conditions, problems in heat transfer, multiphase fluid flow and combustion rates arise. For example, at low temperatures the combustion process proceeds so slowly that the front cannot be propagated. It is a problem in heat transfer to predict what injection rate of air is necessary to sustain combustion in a particular reservoir. Certain fluid flow aspects of underground combustion have been studied by Wilson, et a13. In the development of some of the flow equations, assumptions of adiabatic combustion were made. Vogel and Krueger1 have devised an analog model of the heat conduction process for a constant temperature cylindrical source moving radially outward in a homogeneous conducting medium. Jenkins and Ramey7, in a discussion of the Vogel and Krueger paper, present an analytical solution of a heat conduction problem related to problems considered by Vogel and Krueger. In the present paper an idealized model of the heat conduction problem is considered, which is more general than the model of Vogel and Krueger or Jenkins and Ramey. In particular, initial well heating, vertical heat losses and arbitrary frontal velocities are included. Equations for the temperature are obtained in terms of integrals. These integrals have been evaluated numerically for the case of frontal movement corresponding to a constant air injection rate and the case of constant frontal velocity. These results are presented graphically. From these graphs one may estimate conditions under which nearly adiabatic temperatures are obtained. The application of these results requires some knowledge of reservoir thermal properties, combustion rates and residual fuel content. Assuming no vertical losses it is possible to obtain explicit evaluations of these integrals in the linear con- stant velocity case and in the radial case corresponding to a constant air injection rate. PRESENTATION OF RESULTS The geometry of the radial system is illustrated in Fig. 1 where the reservoir is represented as a slab of thickness h. By making an energy balance for an infinitesimal volume, one obtains the following equation. T= x T+F(z.r).........(1) where F (z,r) =HWv1/pc (r-r1), if z h/2 = 0, if z >h/2 . In Eq. 1, V- represents the Laplacian operator and 8 is the Dirac delta function. Eq. 1 is the well-known diff-sion equation with a source term and may be applied to a linear system. For example, if the source is moving in the direction of the x axis, then the argument of the delta function is x - 1,. In deriving Eq. 1 the following approximations were made concerning the actual combustion process: (1) all heat transfer is by conduction in a homogeneous medium, (2) the formations bounding the reservoir have the same thermal properties as the reservoir, (3) the combustion fuel is consumed instantaneously as the front arrives, (4) there is a constant fuel concentration