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California State University, Northridge Oil Shale: An CALIFORNIA STATE UNIVERSITY, NORTHRIDGE OIL SHALE: AN OVERVIEW ) ( A graduate project submitted in partial satisfaction of the requirements for the degree of Master of Science 1n Engineering by John Page ------- June, 1979 The Graduate Project of John Page is approved: Jon H. California State University, Northridge ii PREFACE This report deals with various aspects of the oil shale industry in the United States today. Only that part of the industry which relates to above ground retorting is focused on. In situ technology will not be discussed as such, but will be included only insofar as it adds con- tinuity to this report. The in situ process is not focused on because it is still largely in the study phase, is not yet technically ready for commercialization, and forms a small part of the overall oil shale industry. There is much published literature which focuses on particular facets of oil shale. One can find information on retorting, costs, environmental aspects, and a host of other specialized topics. However, works which treat oil shale on the whole are few. It is the purpose of this report to fill such a gap; to give the reader an up-to-date overview of the salient aspects of the technology, problems and prospects for the industry. ].ii TABLE OF CONTENTS _DPaae__ PREFACE iii LIST OF TABLES vi LIST OF FIGURES viii ABSTRACT ix Chapter I RESERVES 1 II RETORTING 6 Bureau of Mines Gas-Combustion Retort 7 Union Oil Company Process 17 The TOSCO-II Process 21 The Paraho Process 24 III REFINING 30 Union Oil Company 30 Applied Systems Corporation 31 Performance Characteristics of the Shale Oil-Based Fuels Refined at Gary Western 47 IV ENVIRONMENTAL ASPECTS OF OIL SHALE DEVELOPMENT 51 Physiography and Climate 51 Water Requirements 52 Water Availability 53 Waste ll/"ater 54 Air Quality 55 Spent Shale Disposal 61 v COSTS OF A COMMERCIAL OIL SHALE FACILITY 67 VI PLANS FOR COMMERCIAL DEVELOPMENT 75 Colony Development Operation 75 Union Oil Company 76 Paraho 76 Superior Oil Shale Project 78 C-b Oil Shale Venture 82 Rio Blanco Oil Shale Company 83 White RiveT Shale Project . 84 iv Industry's Views on Commercialization . 85 VII THE FUTURE 87 FOOTNOTES . 89 REFERENCES 100 LIST OF TABLES Table 1 Typical Composition of Oil Shale Sections Averaging 25 Gallons of Oil Per Ton in the Mahogany Zone of Colorado and Utah 2 2 Shale Oil Resources in the Green River Formation, in Billions of Barrels . 5 3 Operating Conditions for Evaluation Runs on 150 tpd Plant 14 4 General Data Summary, Evaluation Runs on the 150 tpd Plant 14 5 Raw and Retorted Shale Properties, Evaluation Runs on the 150 tpd Plant 15 6 Product Oil Properties, Evaluation Runs on the 150 tpd Plant 16 ..., I Product Gas Properties, Evaluation Runs on the 150 tpd Plant 16 8 Product Oil Properties for Union Oil Retorts, Models A and B 20 9 Companies Participating in the Paraho Oil Shale Demonstration Project 10 Paraho Retorting Gas Properties (Dry Basis) 28 11 Paraho Retorting Product Oil Quality 29 12 Product Yields from Refining of Commercial Shale Oil 13 Product Properties from Refining of Commercial Shale Oil 34 14 Paraho Retort Crude Shale Oil 35 15 True Boiling Point Distillation of Shale Oil Crude . 16 Physical and Chemical Properties of Nato Gasoline (Blend Line) 42 vi Table 17 Physical and Chemical Properties of JP-4 43 18 Physical and Chemical Properties of JP-5/Jet A 44 19 Physical and Chemical Properties of Diesel Fuel Marine and DF-2 . 45 20 Physical and Chemical Properties of Heavy Fuel Oil 46 21 Emissions and Fuel Economy--Shale Gasoline . 48 22 Energy Processes: Water Consumption Comparison 53 23 Federal Primary Ambient Air Quality Standards 57 24 State Ambient Air Quality Standards 58 25 Results of Modeling Studies for Facilities Producing Between 45,000 and 62,500 Barrels/Dav 60 26 Chemical Properties of Union Oil Spent Shale 62 27 Inorganic Ions Leachable from Freshly Retorted Shales (Kgs/tonne)--Based on Laboratory Tests 62 28 1971 Species Plots 64 29 Capital Investment Summary 69 30 Estimated Annual Operating Cost 70 31 Breakdown of Investment for the Colony Project 72 32 Breakdown of Operating Costs for the Colony Project . 73 33 Oil Shale Reserves, Prototype Tracts 81 vii LIST OF FIGURES Figure 1 Distribution of oil shale in the Green River Formation, Colorado, Utah and Wyoming 4 2 Gas-combustion process 8 3 Isothermal cross section, 6 tpd retort 10 4 Bed temperature profile, 6 tpd gas retort 11 5 Basic 150 tpd retort dimensions and thermocouple locations 13 6 Side view of Union B retort 18 7 Flow diagram for Union B retorting process 19 8 Pyrolysis unit TOSCO II process 22 9 Seventeen-story tall semiworks structure at Parachute Creek . 23 10 Paraho retorting, direct mode 26 11 Paraho retorting, indirect mode 12 Refining commercial shale oil, fluid catalytic cracking case 13 Schematic diagram--gasoline processing 39 14 Refining process schematic diagram 41 15 Union Oil Company's experimental 10,000 tons per day oil shale plant 77 16 Map showing general geographic location of the six oil shale tracts . 80 viii ABSTRACT OIL SHALE: AN OVERVIEW by John Page Master of Science in Engineering This report gives an overview of some of the prominent facets of the conventional oil shale industry in the United States today. In situ technology as a separate item is not discussed. Topics covered include oil shale reserves; and the U.S. Bureau of Mines gas-combustion, Union Oil Company, TOSCO-II, and Paraho processes for retorting the oil shale. Refining experiences of the Union Oil Company and Applied Systems Corporation are mentioned, and a description of the performance characteristics of some of the refined products of crude shale oil are presented. Environmental aspects dealt with focus primarily on water, air quality, and spent shale disposal including the 1·evegetation operations of two companies on spent shale. Meeting air quality ix standards is the most difficult environmental problem with which the oil shale industry has to deal. Recent cost estimates for an oil shale facility follow next, and price ranges for shale oil produced today are presented. Although no commercial oil shale facilities are currently under construction, plans by the major corporations which may lead to commercialization in the future are given, along with views by those in industry on the constraints facing commercialization and what can be done to alleviate them. Finally, some reflections on the outlook for future development follow. X CHAPTER I RESERVES Oil shale may be defined as fine-textured sedi- mentary rock containing organic matter which yields sub- stantial quantities of oil by conventional methods of destructive distillation. About 80% of the organic material is finely divided insoluable matter known as kerogen, the 1 2 rema1ncter. cons1st1ng. o·f sou.1 bl e b.1tumen. ' Table 1 gives the composition of typical oil shale from the Mahogany zone of Colorado and Utah. Some oil shales contain appreciable amounts of nahcolite, NaHC0 3 , and dawsonite, NaAl(OH) 2co 3 , both of vihich are sodium carbonate salts. Nahcolite may be processed and refined into baking soda. It also has a high affinity for sulfur dioxide, making it a valuable material for air pollution control. Dawsonite can be processed to yield alumina, the basic material from which alwninium is made, and soda ash (sodium carbonate). Soda ash is used in the manufacture of glass, in the paper and pulp industry, and the production of detergents. Oil shale reserves in the United States are commonly quoted on the basis of the amount of oil, in gallons per ton, which may be derived from them. High grade deposits contain 25 or more gallons per ton. The United States is 1 2 Table 1 Typical Composition of Oil Shale Sections Averaging 25 Gallons of Oil per Ton in the Mahogany Zone of Colorado and Utah3 Weight-percent Organic matter: Content of raw shale 13.8 Ultimate composition: Carbon 80.5 Hydrogen 10.3 Nitrogen 2.4 Sulfur 1.0 Oxygen 5. 8 Total 100.0 Mineral matter: Content of raw shale 86.2 Estimated mineral constituents: Carbonates, principally dolomite 48 Feldspars 21 Quartz 13 Clays, principally illite 13 Analcite 4 Pyrite 1 Total 100 particularly rich in deposits, with known resources of 4400 4 billion barrels oil equivalent. The eastern and central parts of the country contain approximately 250,000 square miles of shale underlain deposits up to 800 feet thick. 5 Known resources are estimated at 400 billion barrels. The average oil yield, however, is low, being less than 10 3 i. gallons per ton. In certain areas deposits 5 to 20 feet thick yield 10 to 20 gallons per ton. Shale deposits with oil yields greater than 25 gallons per ton are very small. In Alaska, oil shale deposits are not well defined, how- ever, those yielding over five gallons per ton are thought to be large. By far the largest known oil shale deposits in the United States lie in the three-state area of Wyoming, Utal1 and Colorado and constitute what is kno1'-Tn as the Green River Formation (Figure 1). Of these three states, Colorado has the highest quality reserves, the Piceance Basin within the state being particularly rich (Table 2). The Mahogany zone which underlies more than 2000 square miles largely in the Piceance Basin contains deposits at least 30 and up to 2000 feet think, yielding on the average 30 gallons per ton of oil shale. So far, mention has been made only of total known reserves. All of these reserves are neither technically nor economically recoverable.
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