Charlene R. Crocker

Surface compositions of carbon sorbents exposed to simulated low-rank coal flue gases

Abstract Bench-scale testing of elemental mercury (Hg0) sorption on selected activated carbon sorbents was conducted to develop a better understanding of the interaction among the sorbent, flue gas constituents, and Hg0. The results of the fixed-bed testing under simulated lignite combustion flue gas composition for activated carbons showed some initial breakthrough followed by increased mercury (Hg) capture for up to ∼4.8 hr. After breakthrough, the Hg in the effluent stream was primarily in an oxidized form (>90%). Aliquots of selected activated carbons were exposed to simulated flue gas containing Hg0 vapor for varying time intervals to explore surface chemistry changes as the initial breakthrough, Hg capture, and oxidation occurred. The samples were analyzed by X-ray photoelectron spectroscopy to determine changes in the abundance and forms of sulfur, chlorine, oxygen, and nitrogen moieties as a result of interactions of flue gas components on the activated carbon surface during the sorption process. The data are best explained by a competition between the bound hydrogen chloride (HCl) and increasing sulfur [S(VI)] for a basic carbon binding site. Because loss of HCl is also coincident with Hg breakthrough or loss of the divalent Hg ion (Hg2+), the competition of Hg2+ with S(VI) on the basic carbon site is also implied. Thus, the role of the acid gases in Hg capture and release can be explained.

The Effect of Coal Combustion Flue Gas Components on Low-Level Chlorine Speciation Using EPA Method 26A

ABSTRACT U.S. Environmental Protection Agency (EPA) Method 26A is the recommended procedure for capturing and speci-ating halogen (X2) and hydrogen halide (HX) stack emissions from combustion sources. Previous evaluation studies of Method 26A have focused primarily on hydrogen chloride (HCl) speciation. Capture efficiency, bias, and the potential interference of Cl2 at high levels (>20 ppm [u,g/m3]) and NH4Cl in the flue gas stream have been investigated. It has been suggested that precise Cl2 measurement and accuracy in quantifying HX or X2 using Method 26A are difficult to achieve at Cl2 concentrations <5 ppm; however, no performance data exist to support this. Coal contains low levels of Cl, in the range of 5-2000 ppmw, which results in the presence of HCl and Cl2 in the products of combustion. HCl is the predominant Cl compound formed in the high-temperature combustion process, and it persists in the gas as the products of combustion cool. Concentrations of Cl2 in coal combustion flue gas at stack temperatures typically do not exceed 5 ppm. For this research, bench-scale experiments using simulated combustion flue gas were designed to validate the ability of Method 26A to speci-ate low levels of Cl2 accurately. This paper presents the results of the bench-scale tests. The effect of various flue gas components is discussed. The results indicate that SO2 is the only component in coal combustion flue gas that has an appreciable effect on Cl2 distribution in Method 26A impingers, and that Method 26A cannot accurately speciate HCl and Cl2 in coal combustion flue gas without modification.

JV TASK 45-MERCURY CONTROL TECHNOLOGIES FOR ELECTRIC UTILITIES BURNING LIGNITE COAL, PHASE I BENCH-AND PILOT-SCALE TESTING

The Energy & Environmental Research Center has completed the first phase of a 3-year, two-phase consortium project to develop and demonstrate mercury control technologies for utilities that burn lignite coal. The overall project goal is to maintain the viability of lignite-based energy production by providing utilities with low-cost options for meeting future mercury regulations. Phase I objectives are to develop a better understanding of mercury interactions with flue gas constituents, test a range of sorbent-based technologies targeted at removing elemental mercury (Hg{sup o}) from flue gases, and demonstrate the effectiveness of the most promising technologies at the pilot scale. The Phase II objectives are to demonstrate and quantify sorbent technology effectiveness, performance, and cost at a sponsor-owned and operated power plant. Phase I results are presented in this report along with a brief overview of the Phase II plans. Bench-scale testing provided information on mercury interactions with flue gas constituents and relative performances of the various sorbents. Activated carbons were prepared from relatively high-sodium lignites by carbonization at 400 C (752 F), followed by steam activation at 750 C (1382 F) and 800 C (1472 F). Luscar char was also steam-activated at these conditions. These lignite-based activated carbons, along with commercially available DARCO FGD and an oxidized calcium silicate, were tested in a thin-film, fixed-bed, bench-scale reactor using a simulated lignitic flue gas consisting of 10 {micro}g/Nm{sup 3} Hg{sup 0}, 6% O{sub 2}, 12% CO{sub 2}, 15% H{sub 2}O, 580 ppm SO{sub 2}, 120 ppm NO, 6 ppm NO{sub 2}, and 1 ppm HCl in N{sub 2}. All of the lignite-based activated (750 C, 1382 F) carbons required a 30-45-minute conditioning period in the simulated lignite flue gas before they exhibited good mercury sorption capacities. The unactivated Luscar char and oxidized calcium silicate were ineffective in capturing mercury. Lignite-based activated (800 C, 1472 F) carbons required a shorter (15-minute) conditioning period in the simulated lignite flue gas and captured gaseous mercury more effectively than those activated at 750 C (1382 F). Subsequent tests with higher acid gas concentrations including 50 ppm HCl showed no early mercury breakthrough for either the activated (750 C, 1382 F) Bienfait carbon or the DARCO FGD. Although these high acid gas tests yielded better mercury capture initially, significant breakthrough of mercury ultimately occurred sooner than during the simulated lignite flue gas tests. The steam-activated char, provided by Luscar Ltd., and DARCO FGD, provided by NORIT Americas, were evaluated for mercury removal potential in a 580 MJ/hr (550,000-Btu/hr) pilot-scale coal combustion system equipped with four particulate control devices: (1) an electrostatic precipitator (ESP), (2) a fabric filter (FF), (3) the Advanced Hybrid{trademark} filter, and (4) an ESP and FF in series, an EPRI-patented TOXECON{trademark} technology. The Ontario Hydro method and continuous mercury monitors were used to measure mercury species concentrations at the inlet and outlet of the control technology devices with and without sorbent injection. Primarily Hg{sup o} was measured when lignite coals from the Poplar River Plant and Freedom Mine were combusted. The effects of activated Luscar char, DARCO FGD, injection rates, particle size, and gas temperature on mercury removal were evaluated for each of the four particulate control device options. Increasing injection rates and decreasing gas temperatures generally promoted mercury capture in all four control devices. Relative to data reported for bituminous and subbituminous coal combustion flue gases, higher sorbent injection rates were generally required for the lignite coal to effectively remove mercury. Documented results in this report provide the impacts of these and other parameters and provide the inputs needed to direct Phase II of the project.

JV Task 90 - Activated Carbon Production from North Dakota Lignite

The Energy & Environmental Research Center (EERC) has pursued a research program for producing activated carbon from North Dakota lignite that can be competitive with commercial-grade activated carbon. As part of this effort, small-scale production of activated carbon was produced from Fort Union lignite. A conceptual design of a commercial activated carbon production plant was drawn, and a market assessment was performed to determine likely revenue streams for the produced carbon. Activated carbon was produced from lignite coal in both laboratory-scale fixed-bed reactors and in a small pilot-scale rotary kiln. The EERC was successfully able to upgrade the laboratory-scale activated carbon production system to a pilot-scale rotary kiln system. The activated carbon produced from North Dakota lignite was superior to commercial grade DARCO{reg_sign} FGD and Rheinbrauns HOK activated coke product with respect to iodine number. The iodine number of North Dakota lignite-derived activated carbon was between 600 and 800 mg I{sub 2}/g, whereas the iodine number of DARCO FGD was between 500 and 600 mg I{sub 2}/g, and the iodine number of Rheinbrauns HOK activated coke product was around 275 mg I{sub 2}/g. The EERC performed both bench-scale and pilot-scale mercury capture tests using the activated carbon made under various optimization process conditions. For comparison, the mercury capture capability of commercial DARCO FGD was also tested. The lab-scale apparatus is a thin fixed-bed mercury-screening system, which has been used by the EERC for many mercury capture screen tests. The pilot-scale systems included two combustion units, both equipped with an electrostatic precipitator (ESP). Activated carbons were also tested in a slipstream baghouse at a Texas power plant. The results indicated that the activated carbon produced from North Dakota lignite coal is capable of removing mercury from flue gas. The tests showed that activated carbon with the greatest iodine number was superior to commercial DARCO FGD for mercury capture. The results of the activated carbon market assessment indicate an existing market for water treatment and an emerging application for mercury control. That market will involve both existing and new coal-fired plants. It is expected that 20% of the existing coal-fired plants will implement activated carbon injection by 2015, representing about 200,000 tons of annual demand. The potential annual demand by new plants is even greater. In the mercury control market, two characteristics are going to dominate the customers buying habit-performance and price. As continued demonstration testing of activated carbon injection at the various coal-fired power plants progresses, the importance of fuel type and plant configuration on the type of activated carbon best suited is being identified.

NICKEL SPECIATION OF URBAN PARTICULATE MATTER

A four-step sequential Ni extraction method, summarized in Table AB-1, was evaluated for identifying and quantifying the Ni species occurring in urban total suspended particulate (TSP) matter and fine particulate matter (<10 {micro}m [PM{sub 10}] and <2.5 {micro}m [PM{sub 2.5}] in aerodynamic diameter). The extraction method was originally developed for quantifying soluble, sulfidic, elemental, and oxidic forms of Ni that may occur in industrial atmospheres. X-ray diffraction (XRD) and x-ray absorption fine structure (XAFS) spectroscopy were used to evaluate the Ni species selectivity of the extraction method. Uncertainties in the chemical speciation of Ni in urban PM{sub 10} and PM{sub 2.5} greatly affect inhalation health risk estimates, primarily because of the large variability in acute, chronic, and cancer-causing effects for different Ni compounds.