EPA-908/4-77-010A Emissions From Synthetic Fuels Production Facilities VOLUME I EXECUTIVE SUMMARY US. Environmental Protection Agenq/ Region Nlll Deni/er, Colorado ------- DCN 77-100-092-01 EMISSIONS FROM SYNTHETIC FUELS PRODUCTION FACILITIES VOLUME I EXECUTIVE SUMMARY September 1977 Prepared for: Environmental Protection Agency Region VIII Denver, Colorado By: J. D. Colley, W. A. Gathman, M. L. Owen Radian Corporation Austin, Texas TS-6a ------- FOREWORD The two volumes comprising this document present a study of emissions from synthetic fuel production facilities performed under EPA Contract No. 68-01-3535. The synthetic fuel production facilities include oil shale and coal extraction, oil shale processing, and coal gasification. This report presents the best available information. Most of the data for the TOSCO II oil shale process have been previously published and represent widely accepted estimates for the process. Accepted published data for the Union Oil and Paraho oil shale processes are not presently available. The emissions from these processes were estimated in this report based upon similar processes and developer information. Accep- ted data for the Lurgi coal gasification process have been pre- viously published. As more information on these processes is released, the contents of this report will be updated or subse- quent reports will be conducted to present these data. This work was conducted under the direction of Mr. Terry L. Thoem, Project Officer, Environmental Protection Agency, Region VIII, Denver, Colorado. This study is comple- mented by another Radian study, "Atmospheric Pollution Potential From Fossil Fuel Resource Extraction, On-Site Processing, and Transportation", EPA-600/2/76-064. The fuel resources consid- ered in that report are coal, oil shale, oil, and gas. 11 ------- ABSTRACT This report was compiled to provide the Environmental Protection Agency with an assessment of multi-media pollutants from oil shale processing and coal gasification facilities. The report examines oil shale and coal extraction methods in addition to fuel conversion processes. Three oil shale conversion processes are considered: the TOSCO II, Para- ho, and Union Oil processes. The Lurgi process is considered for coal gasification. Process descriptions and module defin- itions are presented for each operation. Potential air emis- sions , water effluents, and solid wastes are then identified and quantified for each module. Emissions of trace elements and organics are determined qualitatively. An assessment of resources required to support the production facilities is also included. The overall report is presented in two volumes. Volume I summarizes the objectives, the approach, and the re- sults of the study. Volume II gives detailed descriptions of the methodology and the results. 111 ------- TABLE OF CONTENTS PAGE FOREWORD ii ABSTRACT iii TABLE OF CONTENTS iv LIST OF TABLES v 1.0 INTRODUCTION 1 2.0 OBJECTIVES 2 3.0 APPROACH 3 4.0 RESULTS 6 4.1 Air Emissions 6 4.2 Water Effluents 9 4.3 Solid Wastes 9 4.4 Trace Elements 12 4.5 Trace Organics 14- 5.0 CONCLUSIONS AND RECOMMENDATIONS 16 iv ------- LIST OF TABLES PAGE Table 4-1. Module Air Emission Summaries Table 4-2. Synthetic Fuel Facility Air Emission Summaries 10 Table 4-3. Solid Waste 11 v ------- 1.0 INTRODUCTION A large portion of the Western United States contains vast quantities of coal and oil shale. More than 60% of the nation's strippable coal reserves and essentially all of the attractive oil shale reserves are found in the 6 state EPA Re- gion VIII area. Technology for the conversion of oil shale and coal into synthetic fuels is currently being developed and assessed. Production of synthetic fuels can result in dischar- ges of pollutants to the environment from conversion facilities This study assesses emissions and effluent characteristics, energy recovery, ancillary energy requirements and raw material consumption involved in the production of synthetic fuels from coal and oil shale. The study specifically examines oil shale and coal extraction, oil shale processing, and coal gasifica- tion. Three oil shale conversion processes are studied. They are the TOSCO II process, the Paraho process, and the Union Oil process. The Lurgi gasifier is studied for coal gasifica- tion assessment. ------- 2.0 OBJECTIVES The major objective of this study is to identify and quantify potential pollutants from production facilities for oil shale processing and coal gasification. The operations studied include oil shale and coal extraction and sizing, oil shale retorting (TOSCO II, Paraho, and Union Oil processes), coal gasification (Lurgi process), and shale oil upgrading. Resources required to support the synthetic fuel pro- duction facilities are also assessed. These resources include manpower, water, and ancillary energy. -2- ------- 3.0 APPROACH To assess the various synthetic fuels processes, all readily available information sources were investigated. These information sources include the following: EPA studies and regulations, such as energy conversion studies and new source performance standards, other government studies dealing with energy conversion systems, such as Federal Energy Administration, Council on Environmental Quality, Energy Re- search and Development Administration, and Department of the Interior, publications and private industry com- munications , information retrieval networks, site visits to pilot plant facilities, and Radian inhouse files. After all the applicable information had been extrac- ted from the above information sources it was apparent that suf- ficient information did not exist to adequately assess all the areas of interest. In areas where data were inadequate to quan- tify the pollutants from the synthetic fuels processes, similar processes were studied. For example, very little information is -3- ------- available on air emissions from the Union Oil and Paraho oil shale processes while a detailed assessment of the emissions from the TOSCO II process is available. An estimate of the emissions from the Union Oil and Paraho processes was made by comparing similarities in the operating parameters of these processes with those of the TOSCO II process. Where operating characteristics are dissimilar, similar operations from other industries, such as the petroleum refining industry, were assessed. Additional information on the emissions from the Union Oil process was obtained from the developer. Insufficient data is available to quantify emissions of trace elements, such as selenium, mercury, lead, arsenic, cadmium, beryllium, and antimony, and trace organics, such as benz(a)pyrene. These trace pollutants are of special interest due to their demonstrated adverse health effects. A qualitative determination of trace pollutants from synthetic fuel processes was made by comparing trace pollutant studies for different op- erations and assessing the similarities and differences between the operations. After the necessary information was gathered, a series of standardized modules representing the basic process steps were defined. Emissions and effluents, process energy, ancillary en- ergy and raw material requirements were then quantified for each module. Module sizes were selected to represent "typical" com- mercial installations currently being considered for construction The oil shale modules are sized to produce 8,000 m3/day (50,000 bbl/day) of primary fuels. The coal gasification module is sized for 8 x 106 Nm3/day (250 x 106 scfd) of synthetic natural gas. The modules each produce about 7 x 1010 kcal/day (3 x 10" Btu/ day). Consequently, emissions from the conversion facilities can easily be compared on the basis of energy production rates. -4- ------- Before making such a comparison, however, the following precau- tions should be observed: 1) Energy production rates for the modules are only approximately equal. Comparisons of emissions on the basis of energy produc- tion rates are intended to be used only as general guidelines. 2) The inherent value of products from the processes may be different. The primary fuel produced from oil shale is liquid, while fuel produced from coal gasification is gaseous. These fuels are not equally suitable for all applications. For exam- ple, liquid fuels are presently more ap- propriate for use in the transporation industry. -5- ------- 4.0 RESULTS This section presents a summary of the emissions, effluents and solid wastes from the synthetic fuels production facilities studied. The pollutant rates from the facilities are compared and discussed. 4.1 Air Emissions The impact of a synthetic fuel process is the sum of the impacts of the modules that make up that process. A summary of the emissions from the analyzed modules is presented in Table 4-1. The term "hydrocarbons" in this report refers to volatile organic emissions. Mining The oil shale surface mining module generates more pollutants than the room-and-pillar oil shale mining and the coal surface mining modules. Particulate emissions for oil shale surface mining are mainly due to the large amount of overburden that must be removed to expose the resource. For coal surface mining, a smaller quantity of overburden needs to be removed per energy equivalent of resource recovered. Nitrogen oxide, hydrocarbon, and carbon monoxide emissions from oil shale surface mining are significantly larger than from oil shale room-and-pillar mining. This is primarily due to the assumption that surface mining uses mostly diesel power while room-and-pillar mining uses significant amounts of electric power. -6- ------- TABLE 4-1. MODULE AIR EMISSION SUMMARIES Emissions (kg/day) 1. 2. 3. 4. 5. 6. 7 8. 9. 10. 11. 12. 13. 14. Module Oil Shale-Surface Mining Oil Shale-Room- and-Pillar Mining Oil Shale-Primary Sizing Oil Shale-Secondary and Tertiary Sizing Oil Shale-TOSCO II Retorting Oil Shale-TOSCO II Upgrading Oil Shale-Paraho Retorting Oil Shale-Paraho Upgrading Oil Shale-Union Oil Retorting Oil Shale-Union Oil Upgrading Coal Surface Mining Coal-Lurgi High-Btu Gasification Coal-Lurgi Low-Btu Gasification Coal-Lurgi Medium-Btu Gasification Particulates 31,010 665 245 486 7,652 i90 988 190 683 190 3,794 790 790 790 S02 2,640 -- -- -- 1,587 1,490 1,244 1,490 1,528 460 83 10,970 10,100 9,740 NOX 35,990 2,945 -- -- 15,557 1,378 12,407 1,378 6,788 1,378 1,125 17,930 17,930 17,930 HC 4,170 590 -- -- 2,948 7,659 265 7,659 325 7,659 130 210 210 210 CO 21,590 5,180 -- -- 508 168 425 168 715 168 676 N/A N/A N/A N/A - Not available ------- Oil Shale Retorting The TOSCO II retort indirectly heats oil shale by using heated solids (ceramic balls). The Paraho retort and Union Retort B are assumed to indirectly heat oil shale with heated recycle gas. Emissions from TOSCO II retorting and Paraho retor- ting are very similar except for particulates and hydrocarbons. TOSCO II emits more particulates because the oil shale is more finely crushed and because of an additional heat exchange step for heating the raw oil shale prior to retorting. This heat exchange step is probably also the cause of higher hydrocarbon emissions from TOSCO II. The Union Oil emissions are similar to the Paraho emissions except for NO . Lower NO emissions X X could result from Union Oil's plans to combust only fuel gas for retorting, while the other processes may also use fuel oil and C^ liquid. Oil Shale Upgrading Different retorting methods produce different quali- ties of fuel. Since all the retorting methods are assumed to use indirect heat, the fuels produced that are available for process heat are very similar. Consequently, the upgrading emissions for the processes should be very similar. SOz emis- sions from the Union upgrading steps are less than for TOSCO II and Paraho since Union has no S02 emissions from the sulfur recovery unit because the tail gas is sent to the retorting unit to be combusted. -8- ------- Coal Gasification Emissions from Lurgi high-, medium-, and low-Btu gasifiers are very similar for the same energy output. Differ- ences in the processes do not have a large impact on emissions. Gas production rates for the modules, however, are different. The high-Btu gasifier module is sized for a typical commercial facility. The medium-, and low-Btu gasifier modules produce higher gas rates to achieve the same energy output. Summary Total air emissions from synthetic fuel facilities, based on the sum of the modules, are presented in Table 4-2. In general, oil shale facilities have higher emission rates than coal gasification facilities except for S02 emissions. Surface mining modules of the oil shale facilities contribute the greatest amounts of emissions. 4.2 Water Effluents All of the synthetic fuels processes examined are based on zero discharge of water effluents to the surface water. This design feature has not been established at full scale facilities. Also, the potential impact from the leaching of pollutants into ground water systems, has not yet been de- fined . 4.3 Solid Wastes The amount of solid waste produced by each module is presented in Table 4-3 along with a description of the waste. Surface mining of coal and oil shale produce significant amounts ------- TABLE 4-2. SYNTHETIC FUEL FACILITY AIR EMISSION SUMMARIES 1. 2. 3. 4. 5. 6. 7. 8. 9. Process Oil Shale-Surface Mining/TOSCO II Oil Shale-Surface Mining/Paraho Oil Shale-Surface Mining/Union Oil Oil Shale-Room-and-Pillar/TOSCO II Oil Shale-Room-and-Pillar/Paraho Oil Shale-Room-and-Pillar/Union Oil Coal-Surface Mining/Lurgi High-Btu Coal-Surface Mining/Low-Btu Coal-Surface Mining/Medium-Btu Emissions (kg/day) Particulates S02 NOX HC CO 38,852 5,717 52,925 14,777 22.266 32,188 5,374 49,775 12,094 22,183 31,883 4,628 44,156 12,154 22,473 8,507 3,077 19.B80 11,197 5,856 1,843 2,734 16,730 8,514 5,773 1,538 1,988 11,111 8,574 6,063 4.584 11,053 19,055 340 676* 4,584 10.183 19.055 340 676* 4,584 9,823 19,055 340 676* "'•"Includes only CO emissions for coal surface mining. ------- TABLE 4-3. SOLID WASTE Module Solid Waste (Metric Tons/Day) Composition 1. Oil Shale-Surface Mining 65,000 Overburden 2. Oil Shale-Room-and-Pillar Mining 3. Oil Shale-Secondary and Tertiary Sizing 4. Oil Shale-TOSCO II 49,380 Processed shale/softener sludge/spent catalyst 5. Oil Shale-Paraho 49,380 Processed shale/softener sludge/spent catalyst 6. Oil Shale-Union Oil 48,500 Processed shale/softener sludge/spent catalyst 7. Coal-Surface Mining 8. Coal-Lurgi High-Btu Gasifier 42,700 5,940 Overburden Gasifier ash/softener sludge/spent catalyst 9. Coal-Lurgi Low-Btu Gasifier 5,470 Gasifier ash/softener sludge/spent catalyst 10. Coal-Lurgi Medium-Btu Gasifier 5,280 Gasifier ash/softener sludge/spent catalyst ------- of overburden waste material. Oil shale processing also gener- ates large quantities of solid waste. Disposal of processed shale may be a significant problem unless careful processed shale management is undertaken. The slightly smaller solid waste gen- eration by the Union Oil process is solely due to the assumption that the Union Oil process uses a higher grade oil shale. This assumption is based on available data for the processes. 4. 4 Trace Elements Quantitative information on trace elements from oil shale processing and coal gasification is currently unavailable. Consequently, the fate of trace elements is qualitatively dis- cussed. Oil Shale Processing Information on the fate of trace elements from pro- cesses similar to oil shale processing was assessed. A chemical equilibrium program was used to predict the behavior of trace elements in oil shale processing. The results show that the fol- lowing trace elements are expected to volatilize in the oil shale retort: antimony cadmium mercury arsenic germanium selenium boron lead tin These trace elements will tend to become enriched in the shale oil. Thus, while most of the trace elements will be removed in subsequent shale oil processing, these trace elements will become air emissions when the shale oil is refined or combusted. -12- ------- The study also indicates that the following trace elements tend to stay in the processed shale: barium copper nickel beryllium manganese uranium chromium molybdenum zinc cobalt These trace elements may be leached from processed shale and enter ground water systems if the processed shale is improperly disposed. Coal Gasification Available information on the fate of trace elements from coal gasification and processes with similar operating con- ditions was assessed. Studies including the Equilibrium Program predict that the following trace elements volatilize in the gasifier: antimony fluorine phosphorus arsenic lead selenium bromine mercury tellurium cadmium These trace elements will tend to become enriched in the synthe- sis gas. Subsequent processing of the synthesis gas may remove some of these elements, but those that remain will become air emissions as the gas is combusted as fuel. The studies also indicate that the following trace elements tend to remain in the gasifier ash; -13- ------- barium copper tin beryllium manganese uranium cadmium molybdenum vanadium chromium nickel zinc cobalt These trace elements may be leached from ash and enter ground water systems if the gasifier ash is disposed of improperly. 4.5 Trace Organics Quantitative information on trace organics such as benz(a)pyrene from oil shale processing and coal gasification is currently unavailable. Therefore, the fate of these trace organics is qualitatively discussed. Oil Shale Processing Fugitive air emissions of trace organics such as polycyclic aromatic hydrocarbons, including benz(a)pyrene, are a potential problem in oil shale processing. There is no data, however, to indicate that these fugitive emissions are any worse than those incurred at a petroleum refinery. A potential problem exists that is unique to processed oil shale disposal. Preliminary studies indicate that benz(a)- pyrene is present in processed shale and can be leached from car- bonaceous deposits on processed shale by saline water. This in- dicates that trace organics such as benz(a)pyrene may be intro- duced into ground water systems if processed shale is improperly ^•i sposed. -14- ------- Coal Gasification Data on trace organics from coal gasification is in- adequate. However, examination of similar processes such as coal combustion and coal coking indicate that trace organics such as benz(a)pyrene are likely to be present in coal gasifier tars. There is also the possibility that trace organics may enter the cooling water system through heat exchanger equipment leaks. They would then be concentrated and emitted from the cooling system. -15- ------- 5.0 CONCLUSIONS AND RECOMMENDATIONS The following conclusions result from this study: 1) For equivalent energy outputs, oil shale processing facilities using surface mining emit greater quantities of hydro- carbons, particulates, NO . and CO than X coal gasification facilities. 2) Oil shale surface mining is the greatest source of particulates, N0x, and CO. Particulate and NOX emission rates for oil shale facilities using room-and-pillar mining are reduced to levels similar to coal gasification facilities. 3) Of the oil shale processes studied, the TOSCO II process has the highest emis- sion rates of hydrocarbons and particu- lates. 4) SOz emissions are higher from coal gasifi- cation facilities than oil shale processing facilities. 5) Air emissions and water effluents may contain trace elements and organics from both oil shale processing and coal gasi- fication. 6) The quantity of solid wastes produced in the process is large, especially for oil -16- ------- shale processing. Improper disposal of processed oil shale and coal gasifier ash may result in the leaching of trace elem- ents and organics into ground water systems. Processed oil shale, in particular, may be a source of benz(a)pyrene. 7) Water effluents from the processes will be negligible if they are operated in the "zero discharge" mode. "Zero discharge", however, has not yet been demonstrated on a commercial scale. As a result of the study, the following recommendations for future work have been identified: 1) Sampling of EPA criteria pollutants from all the systems studied is recommended. Pilot plant and prototype operations should be sampled before a widespread industry is developed. 2) The data are insufficient on trace element and organic emissions and effluents for all the processes studied. Data should be gathered from existing facilities. A soph- isticated sampling plan should be developed to ascertain the ultimate fate of these pollutants in the environment. 3) The assumption of "zero discharge" of water effluents from the synthetic fuels processes is a critical parameter in -17- ------- this study. The credibility of the basis of this assumption should be established for the processes by further modeling of the aqueous water systems to establish an optimum water reuse strategy. The merit of treating effluents to a quality that may be discharged should also be in- vestigated. Facilities will be located in water-short areas. Removal of water for plant consumption will deplete surface streams. The resultant increase of total dissolved solids in the streams may produce an environmental impact. 4) The environmental impact of alternate synthetic fuels processes such as in-situ oil shale recovery and coal gasification should be assessed and compared with more conventional methods. -18- U-U.S. Government Printing Office: 1977-781-335/119 Region ------- ERRATA EPA-908/4-77-010A Emissions from Synthetic Fuels Production Facilities - Volume I Executive Summary Table 4-1 Module Air Emissions Summaries p. 7 1. Oil Shale Surface Mining Emissions (Kg/day) Parti culate's 5038 S02 640 NOX 8700 HC 1000 CO 5200 Table 4-2 Synthetic Fuel Facility Air Emission Summaries p-10 Emissions (Kg/day) Particulates SO? NOY HC CO 1. Oil Shale-Surface Mining/ 13,611 3,717 25,635 11,607 5,876 TOSCO II 2. Oil Shale-Surface Mining/ 6,461 3,374 22,485 8,924 5,793 Paraho 3. Oil Shale - Surface Mining/ 6,156 2,628 16,866 8,984 6,083 Union Oil EPA-908/4-77-01 OB Emissions from Synthetic Fuels Production Facilities - Volume II Report Table 2.1-2 Summary of Environmental Impact from Surface Mining of Oil Shale-p.9 Parti culates SO? NOY HC CC^ Air emissions (Kg/day) 5,038 640 8,700 1,000 5,200 ------- UNITED STATES ENVIRONMENTAL PROTECTION AGENCY REGION VIII I860 LINCOLN STREET DENVER, COLORADO 8O2O3 Dear Colleague: I am transmitting the enclosed report "Emissions from Synthetic Fuels Production Facilities" (EPA-908/4-77-010A) for your information and use. This report is one of a series of publications resulting from programs administered and performed by the EPA Office of Energy Activities. The enclosed report was performed by the contractual agreement with Radian Corporation. Special credit is recognized to the EPA Office of Energy, Minerals, and Industry for providing the funding for this project. The subject report is published in two parts—an executive summary and a fully detailed report. The study was initiated in order to provide the EPA with an assess- ment of the multi-media pollutants emanating from oil shale and coal gasification facilities and their associated resource extraction activities. Three oil shale conversion processes—TOSCO II, Paraho, and Union—are investigated. The Lurgi coal gasification process is studied. Extraction processes studied include both surface and under- ground operations. Process descriptions, resource characteristics, in addition to the potential air emissions, (including fugitive losses) water effluents and solid wastes generated are presented in the report. Emissions of trace inorganic elements and organic compounds are presented. Net energy efficiency has also been calculated and discussed. An attempt to relate ambient air or water quality concentrations has not been performed. Availability, reliability, and accuracy of data pertaining to this study was difficult to assess, but in general it was felt that the information included in this report was the most current as of early 1977. Since that time other oil shale processes including the Superior ------- 1977. Since that time other oil shale processes including the Superior multi-mineral recovery and the modified in-situ process have been promoted for potential commercialization. These processes should be the subject of a similar analysis such as is performed in the enclosed report. Conclusions which may be drawn from this study include. 1. For equivalent energy outputs, oil shale processing facilities using surface mining emit greater quantities of hydrocarbons, particulates, NOX, and CO than coal gasification facilities. 2. Oil shale surface mining is the greatest source of particulates. NOX, and CO. Particulate and NOX emission rates for oil shale facilities using room-and-pillar mining are reduced to levels similar to coal gasification facilities. 3. Of the oil shale processes studies, the TOSCO II process has the highest emission rates of hydrocarbons and particulates. 4. S02 emissions are higher from coal gasification facilities than oil shale processing facilities. 5. The environmental impact of alternate synthetic fuels processes such as in-situ oil shale recovery and coal gasification should be assessed and compared with more conventional methods. If you should have any questions regarding this report please contact me or members of my staff. For additional copies of this report or for information regarding other publications resulting from the Office of Energy Activities Energy/Environment Program please contact Ms. Betty Thalhofer (303-837-5914) of my staff. Sincerely, Cooper H. Wayman (I Director " Office of Energy Activities Enclosure ------- |