United States Environmental Protection Agency Industrial Environmental Research Laboratory Research Triangle Park NC 27711 Research and Development EPA-600/S7-84-092 Oct. 1984 &ER& Project Summary Environmental Assessment: Source Test and Evaluation Report—Riley Gas Producer M. R. Fuchs, R. A. Magee, and P. M. Jeans In December 1979, Riley Stoker Corporation conducted a test of the Riley Gas Producer, fueled by North Dakota (Indianhead) lignite. The test, at Riley Stoker's research center in Worcester, MA, was sponsored jointly by Riley Stoker and American Natural Service Company of Detroit, Ml. Radian Corporation performed a Source Test and Evaluation (STE) of the Gas Pro- ducer as part of EPA's program to define and evaluate the environmental effects of low-Btu gasification. The results of the STE are presented in this report. The STE involved characterization ot all inputs and outputs of the Gas Pro- ducer. Material balances were also developed. The output streams included the product gas, ash pan water, cyclone dust, and gasifier ash. The results in- dicate that all output streams have some potential for environmental con- cern, as either fugitive emissions (prod- uct gas) or discharge streams (dust, ash, ash pan water). Analyses of the leachates of the gasifier ash and cyclone dust showed that they were nonhaz- ardous according to Resource Conser- vation and Recovery Act protocol and standards. This Project Summary was developed by EPA's Industrial Environmental Re- search Laboratory. Research Triangle Park, NC. to announce key findings of the research project that is fully docu- mented in a separate report of the same title (see Project Report ordering infor- mation at back). Introduction Radian Corporation is under contract to the EPA to perform a comprehensive environmental assessment of low- and medium-Btu coal gasification. This pro- gram includes the performance of Source Tests and Evaluations (STEs) to gather data for the assessment of viable low- and medium-Btu gasification systems. This report, a Source Test and Evalua- tion Report (STER), gives results of an environmental assessment of the Riley Gas Producer. Riley Stoker Corporation, the Riley Gas Producer licensor, operates a commercial-scale pilot plant at its research center in Worcester, MA. The test program, commissioned by American Natural Service Company (ANSC) of De- troit, Ml, was conducted in December 1979. Radian Corporation performed the STE during this period. Test Overview The STE was designed to collect data pertinent to the environmental assess- ment of the Gas Producer. For the most practical application of the results, testing was performed under steady-state oper- ating conditions. The discharge and pro- cess streams of the gasification process were characterized to determine the potential environmental impact of each. Four streams were characterized: product gas, gasifier ash, cyclone dust, and ash pan water. The product gas was separated into two fractions at 115°C (240°F) by the samp- ling procedure. The separation allows the assessment of potential health and eco- logical effects of fugitive emissions by characterizing the vapors of the product gas which are the most likely source of fugitive emissions. The separation was achieved by collecting the aerosol phase of the product gas in an electrostatic precipitator (ESP) operated at 115°C ------- (240°F). The aerosol phase consists of particulate matter and mist consisting of liquid tars and oils. The vapors of the product gas were collected downstream of the ESP, in a condenser at about 15°C (60°F), followed by either an organics adsorption resin (for collecting organic vapors) or an impinger train (for collecting vaporous trace elements, ammonia, or hydrogen cyanide). The Riley Gas Producer is a modifica- tion of the Morgan Gas Producer, devel- oped in England in the early 1900s. Riley Stoker purchased the licensing rights to the Morgan Gas Producer and has up- dated several design features. The gasi- fier feedstock was North Dakota (Indian- head) lignite supplied by ANSC. (NOTE: In December 1978, EPA characterized a Wellman-Galusha gasification system, using North Dakota (Indianhead) lignite, at the U.S. Bureau of Mines' Twin Cities Metallurgy Research Center at Fort Snel- ling.) Major findings of this program are: • Health effects bioassay tests of both solids and neutral leachates of the gasif ier ash and cyclone dust indicated no adverse health effects; ecological bioassay results of neutral leachates of the gasifier ash and cyclone dust showed significant toxic effects. • Leaching studies of the gasifier ash and cyclone dust, to determine the effects of solid waste disposal, indi- cated that the materials are nonhaz- ardous according to Resource Conser- vation and Recovery Act(RCRA) proto- col and standards. • Over 50 percent of the lignite sulfur is converted to reduced sulfur species in the product gas. • The nitrogen content of the ammonia (NHa) and hydrogen cyanide (HCN) in the product gas is equal to about 26 percent of the I ignite nitrogen content. • Enclosing and pressurizing the coal bin and using nitrogen purge on the gasifier pokehole significantly reduces fugitive emissions from these sources. Results A major concern about using coal and coal-derived fuels in industry centers upon emissions of sulfur dioxide (SO2, nitrogen oxides (NO,), and particulates. While the actual emissions of SOz and NOX due to syngas combustion depend on application, the following correlations can be made. The North Dakota (Indianhead) lignite gasifier feedstock for the 24-hour test had an average sulfur concentration of 0.44 g/106 J (1.02 lb/106 Btu). About 53 (31-100+) percent of the sulfur being fed to the gasifier was converted to reduced sulfur species in the product gas. If 100 percent of the reduced sulfur species in the product gas were converted to S02 during combustion, the resulting SO2 emission level would be 0.49 g/106 J (1.10 lb/106 Btu), based on the heat content of the lignite. The average NHa concentration of the product gas was 7.8 x 105 fjg/Nm3 and the average HCN concentration was 1.8 x 105/ug/Nm3. The nitrogen content of the product gas NH3 and HCN is equal to about 26 percent of the lignite nitrogen content. The particulate loading of the product gas stream was 4.76 x 105 /ug/Nm3, downstream of the cyclone. The partic- ulate was assumed to be of the same composition as the cyclone dust, and the cyclone dust ash content (39.93 percent) was used to calculate the particulate emissions from combustion. Basing the adjusted particulate loading on the heat value of the lignite feedstock, the partic- ulate emission after combustion would be 0.26 g/106 J (0.06 lb/106 Btu). This emission estimate does not consider possible particulate formation resulting from incomplete combustion of tars and oils. Fugitive emissions of hydrocarbons were measured in the area of the gasifier by several methods. Hydrocarbon con- centrations were less than 6.5 x 102 /ug/Nm3 (<1 ppm as CH<). Hydrocarbons were also measured in the off-gases of the nitrogen-pressurized coal bin: the concentrations were 3.2 to 3.9 x 103 fjg/Nm3 (5 to 6 ppm as methane, CH4). Readings of two carbon monoxide (CO) monitors maintained by Riley Stoker were recorded during the sampling: the maximum recorded concentration was 2.7x104//g/Nm3 (24 ppm), with readings generally well below this value. The Occupational Safety and Health Admin- istration (OSHA) permissible exposure limit (PEL) for CO is 5.7 x 104 pg/Nm3 (50 ppm). There is no OSHA regulation for hydrocarbons as a compound class. Pro- pane, the lightest hydrocarbon regulated by OSHA, has a PEL of 1.8 x 106 /ug/Nm3 (1000 ppm). STEs have been performed for a Chap- man low-Btu gasifier (with a bituminous coal feedstock) and a Wellman-Galusha low-Btu gasifier (with an anthracite coal feedstock). The Chapman STER gives results for coal feeder vent gases for hydrocarbons «C7) of 2.5 x 106 /jg/Nm3 and CO of 2 x 107 //g/Nm3. The coal hopper gases at the Wellman-Galusha facility (anthracite) were reported in the STER as 1.4 x 106 /ug/Nm3 CH« and 2.7 x 108 CO. Related values measured at the Riley Gas Producer are several orders of magnitude less. These data demonstrate the relative reduction of fugitive emis- sions achieved by the controls used on the coal bin at the Riley Gas Producer. Trace elements enter the gasification process with the lignite feedstock and are subjected to the high temperatures of the process. Many elements, especially the more volatile ones, are volatilized in the hot areas of the system and may: (1) remain a vapor in the product gas, (2) condense homogeneously, or (3) con- dense on aerosol particulates. Other elements, chemically transformed into gaseous species, are emitted in the product gas. Most trace elements remain in the coal solids and are emitted in the gasifier ash. Even though the majority of most elements are emitted with the solid waste streams, RCRA extraction proce- dures analysis results in the classification of these solids as nonhazardous. Minor and trace elements can be grouped according to the mechanisms by which each is discharged. The elements found primarily in the product gas are considered highly volatile or transfomed into gaseous compounds. Moderately volatile elements, those found predomi- nantly in the cyclone dust or product gas particulate, can be evaluated on the basis of volatilization and recondensation. Ele- ments discharged predominantly in the gasifier ash are considered to be non- volatile. For this STE, an element was con- sidered to be highly volatile if 25 percent or more of its total mass was found in the vapor portion of the product gas. These were: bromine cesium chlorine fluorine gallium iodine mercury selenium silicon sulfur tellurium An element was classified as moder- ately volatile if 25 percent or more of its total mass was found in the cyclone dust and aerosols of the product gas. These were: antimony lead arsenic tin chromium zinc germanium ------- The following elements require addi- tional data to characterize their behavior definitively: I Product Gas O Ash Pan Water • Cyclone Dust I GasifierAsh beryllium iridium bismuth neo- cadmium dymium dysprosium osmium erbium palladium europium platinum gold praeseo- holmium dymium rhenium rhodium ruthenium silver tantalum terbium thallium thulium uranium yterrbium Figure 1 shows the elemental distribu- tions in the discharge streams, in the order of increasing boiling points. In general, as the elemental boiling points increase, the predominance of elemental distribution shifts from the product gas to the gasif ier ash. Although a general trend is evident, there is no direct correlation between elemental boiling point and distribution. The distribution of individual elements in the system depends not only on elemental boiling point, but also on much more complex properties. These may include chemical reactions in the gasifier, the volatility of compounds con- taining the elements, and solubility of compounds in the tars and oils. Gross alpha and beta radioactivities were determined on two samples of lignite, a composite cyclone dust, and a composite gasifier ash. In addition, gam- ma and alpha spectrometry was used for specific isotope analyses of these solid samples. Complete analytical results for gross alpha, beta, and specific isotope analyses are given in the full report. Bioassay tests of the solid gasifier ash and cyclone dust indicated little or no health hazard. A neutral leaching of the two solid streams provided a liquid for bioassay testing that showed a high level of potential ecological hazard. However, subjecting the gasifier ash and cyclone dust to RCRA leaching studies resulted in the solids being classified as nonhazard- ous. 100' 75- 50- >*. 25- F Cl Br I P Hg S As Se Rb Cs K Na ZnMgiBa Li Sb Yb EuCa PbSmMnSnGa Elements in Order of Increasing Boiling Point WO-\ 75H 50H 25- At Cr B CuDyScNi BeTbiGcCo Y Gd Fe V Pr Ti CeLaZr U ThNbMoW Elements in Order of Increasing Boiling Point Figure 1. Stream elemental distributions or percentage of combined discharge streams. ------- M. P. Fuchs, R. A. Magee, and P. M. Jeans are with Radian Corporation, Austin, TX 78766. William J. Rhodes is the EPA Project Officer (see below). The complete report, entitled "Environmental Assessment: Source Test and Evaluation Report—Riley Gas Producer," (Order No. PB 84-246 396; Cost: $31.00, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Industrial Environmental Research Laboratory U.S. Environmental Protection Agency Research Triangle Park, NC 27711 * U.S. GOVERNMENT PRINTING OFFICE; 1984 — 659-016/7839 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 Official Business Penalty for Private Use $300 ------- |