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Title: The Homogeneus Forcing of Mercury Oxidation to provide Low-Cost Capture

Abstract

Trace amounts of mercury are found in all coals. During combustion, or during thermal treatment in advanced coal processes, this mercury is vaporized and can be released to the atmosphere with the ultimate combustion products. This has been a cause for concern for a number of years, and has resulted in a determination by the EPA to regulate and control these emissions. Present technology does not, however, provide inexpensive ways to capture or remove mercury. Mercury that exits the furnace in the oxidized form (HgCl{sub 2}) is known to much more easily captured in existing pollution control equipment (e.g., wet scrubbers for SO{sub 2}), principally due to its high solubility in water. Work funded by DOE has helped understand the chemical kinetic processes that lead to mercury oxidation in furnaces. The scenario is as follows. In the flame the mercury is quantitatively vaporized as elemental mercury. Also, the chlorine in the fuel is released as HCl. The direct reaction Hg+HCl is, however, far too slow to be of practical consequence in oxidation. The high temperature region does supports a small concentration of atomic chlorine. As the gases cool (either in the furnace convective passes, in the quench prior to coldmore » gas cleanup, or within a sample probe), the decay in Cl atom is constrained by the slowness of the principal recombination reaction, Cl+Cl+M{yields}Cl{sub 2}+M. This allows chlorine atom to hold a temporary, local superequilibrium concentration . Once the gases drop below about 550 C, the mercury equilibrium shifts to favor HgCl{sub 2} over Hg, and this superequilibrium chlorine atom promotes oxidation via the fast reactions Hg+Cl+M{yields}HgCl+M, HgCl+Cl+M{yields}HgCl{sub 2}+M, and HgCl+Cl{sub 2}{yields}HgCl{sub 2}+Cl. Thus, the high temperature region provides the Cl needed for the reaction, while the quench region allows the Cl to persist and oxidize the mercury in the absence of decomposition reactions that would destroy the HgCl{sub 2}. Promoting mercury oxidation is one means of getting moderate-efficiency, 'free' mercury capture when wet gas cleanup systems are already in place. The chemical kinetic model we developed to describe the oxidation process suggests that in fuel lean gases, the introduction of trace amounts of H{sub 2} within the quench region leads to higher Cl concentrations via chain branching. The amount of additive, and the temperature at the addition point are critical. We investigated this process in a high-temperature quartz flow reactor. The results do indicate a substantial amount of promotion of oxidation with the introduction of relatively small amounts of hydrogen at around 1000 K ({approx}100 ppm relative to the furnace gas). In practical systems the source of this hydrogen is likely to be a small natural gas steam reformer. This would also produce CO, so co-injection of CO was also tested. The CO did not provide any additional promotion, and in some cases led to a reduction in oxidation. We also examined the influence of NO and SO{sub 2} on the promotion process. We did not see any influence under the conditions examined. The present results were for a 0.5 s, isothermal plug flow environment. The next step should be to determine the appropriate injection point for the hydrogen and the performance under realistic temperature quench conditions. This could be accomplished first by chemical kinetic modeling, and then by tunnel flow experiment.« less

Authors:
;
Publication Date:
Research Org.:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
966369
DOE Contract Number:  
FG26-03NT41808
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
01 COAL, LIGNITE, AND PEAT; 03 NATURAL GAS; 08 HYDROGEN; CHLORINE; COAL; COMBUSTION; COMBUSTION PRODUCTS; DIRECT REACTIONS; GASES; HYDROGEN; KINETICS; MERCURY; NATURAL GAS; OXIDATION; POLLUTION CONTROL EQUIPMENT; RECOMBINATION; SCRUBBERS; SOLUBILITY; TRACE AMOUNTS; US EPA

Citation Formats

Kramlich, John, and Castiglone, Linda. The Homogeneus Forcing of Mercury Oxidation to provide Low-Cost Capture. United States: N. p., 2007. Web. doi:10.2172/966369.
Kramlich, John, & Castiglone, Linda. The Homogeneus Forcing of Mercury Oxidation to provide Low-Cost Capture. United States. https://doi.org/10.2172/966369
Kramlich, John, and Castiglone, Linda. Sat . "The Homogeneus Forcing of Mercury Oxidation to provide Low-Cost Capture". United States. https://doi.org/10.2172/966369. https://www.osti.gov/servlets/purl/966369.
@article{osti_966369,
title = {The Homogeneus Forcing of Mercury Oxidation to provide Low-Cost Capture},
author = {Kramlich, John and Castiglone, Linda},
abstractNote = {Trace amounts of mercury are found in all coals. During combustion, or during thermal treatment in advanced coal processes, this mercury is vaporized and can be released to the atmosphere with the ultimate combustion products. This has been a cause for concern for a number of years, and has resulted in a determination by the EPA to regulate and control these emissions. Present technology does not, however, provide inexpensive ways to capture or remove mercury. Mercury that exits the furnace in the oxidized form (HgCl{sub 2}) is known to much more easily captured in existing pollution control equipment (e.g., wet scrubbers for SO{sub 2}), principally due to its high solubility in water. Work funded by DOE has helped understand the chemical kinetic processes that lead to mercury oxidation in furnaces. The scenario is as follows. In the flame the mercury is quantitatively vaporized as elemental mercury. Also, the chlorine in the fuel is released as HCl. The direct reaction Hg+HCl is, however, far too slow to be of practical consequence in oxidation. The high temperature region does supports a small concentration of atomic chlorine. As the gases cool (either in the furnace convective passes, in the quench prior to cold gas cleanup, or within a sample probe), the decay in Cl atom is constrained by the slowness of the principal recombination reaction, Cl+Cl+M{yields}Cl{sub 2}+M. This allows chlorine atom to hold a temporary, local superequilibrium concentration . Once the gases drop below about 550 C, the mercury equilibrium shifts to favor HgCl{sub 2} over Hg, and this superequilibrium chlorine atom promotes oxidation via the fast reactions Hg+Cl+M{yields}HgCl+M, HgCl+Cl+M{yields}HgCl{sub 2}+M, and HgCl+Cl{sub 2}{yields}HgCl{sub 2}+Cl. Thus, the high temperature region provides the Cl needed for the reaction, while the quench region allows the Cl to persist and oxidize the mercury in the absence of decomposition reactions that would destroy the HgCl{sub 2}. Promoting mercury oxidation is one means of getting moderate-efficiency, 'free' mercury capture when wet gas cleanup systems are already in place. The chemical kinetic model we developed to describe the oxidation process suggests that in fuel lean gases, the introduction of trace amounts of H{sub 2} within the quench region leads to higher Cl concentrations via chain branching. The amount of additive, and the temperature at the addition point are critical. We investigated this process in a high-temperature quartz flow reactor. The results do indicate a substantial amount of promotion of oxidation with the introduction of relatively small amounts of hydrogen at around 1000 K ({approx}100 ppm relative to the furnace gas). In practical systems the source of this hydrogen is likely to be a small natural gas steam reformer. This would also produce CO, so co-injection of CO was also tested. The CO did not provide any additional promotion, and in some cases led to a reduction in oxidation. We also examined the influence of NO and SO{sub 2} on the promotion process. We did not see any influence under the conditions examined. The present results were for a 0.5 s, isothermal plug flow environment. The next step should be to determine the appropriate injection point for the hydrogen and the performance under realistic temperature quench conditions. This could be accomplished first by chemical kinetic modeling, and then by tunnel flow experiment.},
doi = {10.2172/966369},
url = {https://www.osti.gov/biblio/966369}, journal = {},
number = ,
volume = ,
place = {United States},
year = {2007},
month = {6}
}