John H. Pavlish

Review of advances in combustion technology and biomass cofiring

Advances in combustion technology will be adopted only when they reduce cost and can be implemented with acceptable technical risk. Apart from technical risk, future decisions on new power plants will be principally influenced by trends in fuel cost, the efficiency and capital cost of new generating technologies, and environmental and regulatory policies including possible carbon taxes. The choice of fuel and generating technology for new power plants is influenced by an increasingly complex combination of interrelated factors: (1) current and future governmental polices on restructuring and deregulation of utilities, and environmental regulations that in the future could include taxes on carbon emissions; (2) macroeconomic factors such as proximity to load centers, electrical transmission lines, plant capital investment, delivered fuel cost, and fuel price stability; and (3) the state of development of new generating and environmental control technologies and the associated benefits and risks involved in their deployment, which are strongly related to fuel properties. This paper describes three advanced high-efficiency power systems for which the EERC has performed supporting research and development: (1) a coal-fired supercritical steam boiler with advanced emission controls; (2) an indirectly fired combined cycle using compressed air as the working fluid in a gas turbine (GT), fired either on coal alone or on coal and natural gas; and (3) two versions of a hybrid gasifier-pressurized fluidized-bed combustor (PFBC) system.

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.

Fate of hazardous air pollutants in oxygen-fired coal combustion with different flue gas recycling.

Experiments were performed to characterize transformation and speciation of hazardous air pollutants (HAPs), including SO(2)/SO(3), NO(x), HCl, particulate matter, mercury, and other trace elements in oxygen-firing bituminous coal with recirculation flue gas (RFG) from 1) an electrostatic precipitator outlet or 2) a wet scrubber outlet. The experimental results showed that oxycombustion with RFG generated a flue gas with less volume and containing HAPs at higher levels, while the actual emissions of HAPs per unit of energy produced were much less than that of air-blown combustion. NO(x) reduction was achieved in oxycombustion because of the elimination of nitrogen and the destruction of NO in the RFG. The elevated SO(2)/SO(3) in flue gas improved sulfur self-retention. SO(3) vapor could reach its dew point in the flue gas with high moisture, which limits the amount of SO(3) vapor in flue gas and possibly induces material corrosion. Most nonvolatile trace elements were less enriched in fly ash in oxycombustion than air-firing because of lower oxycombustion temperatures occurring in the present study. Meanwhile, Hg and Se were found to be enriched on submicrometer fly ash at higher levels in oxy-firing than in air-blown combustion.

Effects of Sulfur Dioxide and Nitric Oxide on Mercury Oxidation and Reduction under Homogeneous Conditions

Abstract This paper is particularly related to elemental mercury (Hg0) oxidation and divalent mercury (Hg2+) reduction under simulated flue gas conditions in the presence of nitric oxide (NO) and sulfur dioxide (SO2). As a powerful oxidant and chlorinating reagent, Cl2 has the potential for Hg oxidation. However, the detailed mechanism for the interactions, especially among chlorine (Cl)-containing species, SO2, NO, as well as H2O, remains ambiguous. Research described in this paper therefore focused on the impacts of SO2 and NO on Hg0 oxidation and Hg2+ reduction with the intent of unraveling unrecognized interactions among Cl species, SO2, and NO most importantly in the presence of H2O. The experimental results demonstrated that SO2 and NO had pronounced inhibitory effects on Hg0 oxidation at high temperatures when H2O was also present in the gas blend. Such a demonstration was further confirmed by the reduction of Hg2+ back into its elemental form. Data revealed that SO2 and NO were capable of promoting homogeneous reduction of Hg2+ to Hg0 with H2O being present. However, the above inhibition or promotion disappeared under homogeneous conditions when H2O was removed from the gas blend.

Organic sulfur and hap removal from coal using hydrothermal treatment

Abstract Coal is still the major source of power for electrical generation worldwide and will continue to be in the foreseeable future. However, the inorganic elements in coal that qualify as hazardous emissions upon combustion of the coal become an increasingly important concern. Primary emphasis has been on postcombustion cleanup of these emissions, with no technology achieving overwhelming success. The precombustion technique reported here shows promise for removing trace elements as well as sulfur prior to burning the coal. This study shows that hydrothermal treatment need not be carried out at extreme conditions to effect such removal. The sulfur content and selected trace elements of some coals are reduced by 50% or more by water at conditions above the critical temperature but below the critical pressure. The study also shows that the technique was more effective on some coals than others. Results from a pilot-scale test are included in addition to bench-scale data.

Evaluating mercury transformation mechanisms in a laboratory - scale combustion system

Mercury speciation measurements during injections of 10 microg/m3 Hg0(g) into a 42-MJ/h combustion system containing gaseous O2-Ar- and O2-N2-rich mixtures indicate that 43 and 55% of the Hg (g) spike was transformed rapidly (< 0.1 s) to Hg2+X(g) within a refractory-lined heat exchanger where gas temperatures decrease from approximately 620 to 200 degrees C. O2(g) is the probable Hg0(g) oxidant (i.e. X = O2-). The apparent formation of HgO(g) involves a heterogeneous reaction with adsorbed Hg0 or O2 on refractory surfaces or a Hg0(g)-O2(g) reaction catalyzed by corundum (Al2O3) and/or rutile (TiO2) components of the refractory. The potential catalytic effects of Al2O3 and TiO2 on Hg0(g) oxidation were investigated by injecting Al2O3 and TiO2 powders into approximately 650 degrees C subbituminous coal (Powder River Basin, Montana, USA) combustion flue gas. On-line Hg0(g) and total mercury measurements indicate, however, that Al2O3 and TiO2 injections were ineffective in promoting the formation of additional Hg2+X(g). Apparently, either the chemically complex flue gas hindered the catalytic effects of Al2O3 and TiO2, or these compounds are simply not Hg0(g) oxidation catalysts.

Mercury mass balances: a case study of two North Dakota power plants.

ABSTRACT The Energy & Environmental Research Center (EERC) conducted a mercury-sampling program to provide data on the quantity and forms of Hg emitted and on the Hg removal efficiency of the existing air pollution control devices at two North Dakota power plants—Milton R. Young Station and Coal Creek Station. Minnkota Power Cooperative, Great River Energy, the North Dakota Industrial Commission, and EPRI funded the project. The primary objective was to obtain accurate measurements of Hg released from each plant, as verified by a material balance. A secondary objective was to evaluate the ability of a mercury continuous emission monitor (CEM) to measure total Hg at the stack. At both plants, speciated Hg measurements were made at the inlets and outlets of both the electrostatic precipi-tators (ESPs) and the flue gas desulfurization (FGD) systems. A Semtech Hg 2000 (Semtech Metallurgy AB) mercury CEM was used to measure the total Hg emissions at the stack in real time. Using these measurements and plant data, the measured Hg concentrations in the coal, FGD slurries, and ESP ash, a Hg mass flow rate was calculated at each sampling location. Excellent Hg mass balances were obtained (±15%). It was also found that the Hg was mostly in the elemental phase (~90%), and the small amount of oxidized Hg that was generated was removed by the FGD systems. Insignificant amounts of particulate-bound Hg were measured at both plants. However, 10-20% of the elemental Hg measured prior to the ESP was converted to oxidized Hg across the ESP. The data show that, at these facilities, almost all of the Hg generated is being emitted into the atmosphere as elemental Hg. Local or regional deposition of the Hg emitted from these plants is not a concern. However, the Hg does become part of the global Hg burden in the atmosphere. Also, the evidence appears to indicate that elemental Hg is more difficult to remove from flue gas than oxidized Hg is.

Status of research on air quality: mercury, trace elements, and particulate matter

The Air Quality Conference reviewed the state of science and policy on the pollutants mercury, trace elements, and particulate matter (PM) in the environment. Critical issues dealing with impacts on health and ecosystems, emission prevention and control, measurement methods, and atmospheric reactions and modeling were addressed. US Secretary of Energy Bill Richardson, in a keynote address discussed challenges to a deregulated power industry posed by the air quality issues of fine particulates, ozone transport, acid gases, hazardous air pollutants, and carbon emissions. The role and importance of sound science to establish environmental policy was clearly emphasized throughout the conference in technical papers; in policy presentations by Senator Kent Conrad (D-ND), Senator Byron Dorgan (D-ND), and Mr. Dirk Forrister, Chairman of the White House Climate Change Task Force; and in the panel discussions.

Issues associated with the use of activated carbon for mercury control in cement kilns

Mercury is a known neurological toxin that the U.S. Environmental Protection Agency (EPA) regulates under the National Emission Standards for Hazardous Air Pollutants (NESHAP) for municipal waste incinerators and medical waste incinerators. Although later vacated by the courts, mercury regulations were also promulgated for coal-fired utilities. Under the existing and proposed NESHAP for the portland cement industry, EPA is proposing to regulate mercury for the portland cement industry for both new and existing cement plants. A substantial body of information has been generated in the coal-fired boiler industry for activated carbon injection control systems. Utilizing this knowledge base and the limited data from the cement industry, issues and opportunities for activated carbon injection to control mercury from cement kilns will be discussed.

Mercury Information Clearinghouse

The Canadian Electricity Association (CEA) identified a need and contracted the Energy & Environmental Research Center (EERC) to create and maintain an information clearinghouse on global research and development activities related to mercury emissions from coal-fired electric utilities. With the support of CEA, the Center for Air Toxic Metals{reg_sign} (CATM{reg_sign}) Affiliates, and the U.S. Department of Energy (DOE), the EERC developed comprehensive quarterly information updates that provide a detailed assessment of developments in the various areas of mercury monitoring, control, policy, and research. A total of eight topical reports were completed and are summarized and updated in this final CEA quarterly report. The original quarterly reports can be viewed at the CEA Web site (www.ceamercuryprogram.ca). In addition to a comprehensive update of previous mercury-related topics, a review of results from the CEA Mercury Program is provided. Members of Canadas coal-fired electricity generation sector (ATCO Power, EPCOR, Manitoba Hydro, New Brunswick Power, Nova Scotia Power Inc., Ontario Power Generation, SaskPower, and TransAlta) and CEA, have compiled an extensive database of information from stack-, coal-, and ash-sampling activities. Data from this effort are also available at the CEA Web site and have provided critical information for establishing and reviewing a mercury standard for Canada that is protective of environment and public health and is cost-effective. Specific goals outlined for the CEA mercury program included the following: (1) Improve emission inventories and develop management options through an intensive 2-year coal-, ash-, and stack-sampling program; (2) Promote effective stack testing through the development of guidance material and the support of on-site training on the Ontario Hydro method for employees, government representatives, and contractors on an as-needed basis; (3) Strengthen laboratory analytical capabilities through analysis and quality assurance programs; and (4) Create and maintain an information clearinghouse to ensure that all parties can keep informed on global mercury research and development activities.