Patent Application
20140145111
The present disclosure relates generally to methods for controlling emissions of hazardous air pollutants, and more particularly, to methods for controlling mercury emissions from wet flue gas desulfurizers and/or controlling corrosion of scrubber equipment.
Many electricity generating units (EGUs) burn fossil fuels to produce electricity. The combustion process produces intense heat and flue gas, which contains hazardous air pollutants (e.g., Hg, CO2, SO2, SO3, HCl). The flue gas is typically scrubbed prior to release into the atmosphere to reduce emissions of the pollutants. Wet flue gas desulfurizers (WFGDs) are one type of scrubber commonly used to reduce emissions. A WFGD contacts the combustion gas with an aqueous alkaline solution. This solution may be composed of magnesium compounds, sodium compounds, and slurries of lime or limestone to capture and neutralize acid gases, such as sulfur dioxide. The aqueous alkaline solution is commonly referred to as “WFGD liquor” or “scrubber liquor.” In a forced oxidation system, oxygen may be introduced into the WFGD liquor to oxidize sulfite to sulfate. In many cases, this forms gypsum (calcium sulfate), as the final byproduct of scrubbing. Other systems may utilize inhibited or natural oxidation scrubbing, which results in sulfite salts or mixed sulfite/sulfate salts as byproduct.
Mercury entering EGUs as a contaminant of the fuel is released during combustion. Combustion gases exiting the boiler may contain mercury in three forms: particulate, oxidized, and elemental. Particulate mercury can be captured by particulate control devices such as electrostatic precipitators (ESPs) and fabric filters (FF). Oxidized mercury is water-soluble and as such, WFGDs can absorb the oxidized mercury from the combustion gas into the liquid phase. Elemental mercury, which is insoluble in water, is difficult to capture using existing air quality control devices. Accordingly, most elemental mercury control measures focus on converting elemental mercury into oxidized mercury. Mechanical methods such as fixed bed catalysts (e.g., SCRs), and chemical additives (e.g., calcium bromide, hydrogen bromide, ammonium chloride) have been developed that oxidize elemental mercury in the gas phase for subsequent capture with a WFGD. The captured mercury leaves the process via WFGD blow down.
As oxidized mercury is water soluble, WFGDs are theoretically capable of capturing nearly 100% of the oxidized mercury in a combustion gas. However, data collected by the Department of Energy (DOE) as well as numerous laboratory and commercial studies have shown lower capture efficiencies. The lower efficiencies are the result of reduction of oxidized mercury to elemental mercury (e.g., Hg2+ to Hg0) within the WFGD scrubber liquor. For example, one reduction reaction involves the oxidation of sulfite by ionic mercury in the WFGD to provide sulfate and elemental mercury. The result is an increase across the WFGD of elemental mercury content in the scrubbed combustion gas, and thus a decrease in total mercury capture as measured from fossil fuel to stack. This reduction of oxidized mercury in the scrubber and subsequent release is known in the industry as mercury re-emission. The loss in WFGD mercury capture efficiency due to mercury re-emission will prevent some EGUs from meeting emissions requirements, necessitating installation of additional capital equipment.
There is a need in the art for improved methods of controlling mercury re-emission, which can supplement or replace current approaches of reducing hazardous air pollutant emissions.
In one aspect, disclosed is a composition, comprising at least two components selected from a mercury re-emission additive; a free radical scavenger; and a polymer dispersant. The composition may comprise a mercury re-emission additive and a free radical scavenger. The composition may comprise a mercury re-emission additive and a polymer dispersant. The composition may comprise a free radical scavenger and a polymer dispersant. The composition may comprise a mercury re-emission additive, a free radical scavenger, and a polymer dispersant.
The mercury re-emission additive may be a polymeric polydithiocarbamate compound.
The mercury re-emission control additive may be an ethylene dichloride ammonia polymer containing from 5 to 55 mole % of dithiocarbamate salt groups.
The mercury re-emission control additive may be a polymer derived from at least two monomers: acrylic-x and an alkylamine, wherein said acrylic-x has the following formula:
wherein X═OR, OH and salts thereof, or NHR2 and wherein R1 and R2 is H or an alkyl or aryl group, wherein R is an alkyl or aryl group, wherein the molecular weight of said polymer is between 500 to 200,000, and wherein said polymer is modified to contain a functional group capable of scavenging one or more compositions containing one or more metals. The functional group capable of scavenging one or more compositions containing one or more metals may be a sulfur containing functional group.
The mercury re-emission control additive may be selected from the group consisting of: a polymeric polydithiocarbamate compound, sodium sulfide, sodium hydrosulfide, sodium bisulfide, a polysulfide, diethyldithiocarbamate or a sodium salt thereof, dimethyldithiocarbamate or a sodium salt thereof, a sodium polythiocarbonate, an inorganic polysulfide or blend, a sodium or calcium salt of 1,3,5-triazine-2,4,6(1H,3H,5H)-trithione, an activated carbon, 2,3-dimercaptopropanol, dimercaptosuccinic acid, 1,8-octanedithiol, 1,2-dithiolane-3-valeric acid, 2-methyl 1,3-dithiolane, mercaptoacetic acid or a sodium salt thereof, and a halogen-containing compound, or any combination thereof.
The free radical scavenger may be selected from the group consisting of: substituted phenols, derivatives of phenylenediamine, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), citric acid, tertiary butylhydroquinone (TBHQ), tocopherols, ascorbic acid, glutathione, lipoic acid, uric acid, and free radical scavenging enzymes, or any combination thereof.
The polymer dispersant may be selected from the group consisting of: polyacrylic acid, polyacrylates, polymaleic acid, maleic anhydride/ethyl acrylate/vinyl acrylate terpolymer and alkyl epoxy carboxylate, phosphinocarboxylic acids, and phosphonocarboxylic acids, or any combination thereof.
The polymer dispersant may be a polyacrylate or a phosphinosuccinate oligomer.
In another aspect, disclosed is a method of controlling mercury re-emission from a combustion process and/or reducing corrosion of equipment used in a combustion process, the method comprising applying to the combustion process at least two components selected from: a mercury re-emission additive; a free radical scavenger; and a polymer dispersant.
The components may be applied to a scrubber liquor of a wet flue gas desulpherizer (WFGD). The percent mercury re-emission from the scrubber liquor may be reduced to 10% or less. The percent mercury re-emission from the scrubber liquor may be reduced to 1% or less.
The mercury re-emission additive may be a polymeric polydithiocarbamate compound.
The mercury re-emission control additive may be an ethylene dichloride ammonia polymer containing from 5 to 55 mole % of dithiocarbamate salt groups.
The mercury re-emission control additive may be a polymer derived from at least two monomers: acrylic-x and an alkylamine, wherein said acrylic-x has the following formula:
wherein X═OR, OH and salts thereof, or NHR2 and wherein R1 and R2 is H or an alkyl or aryl group, wherein R is an alkyl or aryl group, wherein the molecular weight of said polymer is between 500 to 200,000, and wherein said polymer is modified to contain a functional group capable of scavenging one or more compositions containing one or more metals. The functional group capable of scavenging one or more compositions containing one or more metals may be a sulfur containing functional group.
The mercury re-emission control additive may be selected from the group consisting of: a polymericpolydithiocarbamate compounds, sodium sulfide, sodium hydrosulfide, sodium bisulfide, a poly-sulfide, diethyldithiocarbamate or a sodium salt thereof, dimethyldithiocarbamate or a sodium salt thereof, a sodium polythiocarbonate, an inorganic polysulfide or blend, a sodium or calcium salt of 1,3,5-triazine-2,4,6(1H,3H,5H)-trithione, an activated carbon, 2,3-dimercaptopropanol, dimercaptosuccinic acid, 1,8-octanedithiol, 1,2-dithiolane-3-valeric acid, 2-methyl 1,3-dithiolane, mercaptoacetic acid or a sodium salt thereof, and a halogen-containing compound, or any combination thereof.
The free radical scavenger may be selected from the group consisting of: substituted phenols, derivatives of phenylenediamine, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), citric acid, tertiary butylhydroquinone (TBHQ), tocopherols, ascorbic acid, glutathione, lipoic acid, uric acid, and free radical scavenging enzymes, or any combination thereof.
The polymer dispersant may be selected from the group consisting of: polyacrylic acid, polyacrylates, polymaleic acid, maleic anhydride/ethyl acrylate/vinyl acrylate terpolymer and alkyl epoxy carboxylate, phosphinocarboxylic acids, and phosphonocarboxylic acids, or any combination thereof.
The polymer dispersant may be a polyacrylate or a phosphinosuccinate oligomer.
In another aspect, disclosed is a method of reducing mercury re-emission from a combustion process and/or reducing corrosion of equipment used in a combustion process. The method may include dispersing manganese species; inhibiting the formation of persulfate species; or complexing mercury and/or manganese. The method may include at least two of dispersing manganese species; inhibiting the formation of persulfate species; and complexing mercury and/or manganese.
The compositions, methods, and processes are further described herein.
Disclosed herein are compositions and methods for controlling mercury emissions from a scrubber process and/or reducing corrosion of scrubber equipment. The compositions and methods may include at least two components selected from a mercury re-emission additive, a free radical scavenger, and a polymer dispersant. The components may exhibit a synergistic effect for reducing mercury emissions and/or reducing corrosion.
The compositions and methods may control mercury emissions and/or corrosion by targeting one or more chemical species found in a combustion process, and in particular, species that lead to mercury re-emission and/or corrosion. Chemical species that can be targeted include, but are not limited to, persulfate species (S2O82−), manganese species (e.g., Mn4+), mercury species (e.g., Hg0), iron species, and free radical species (e.g., carbon dioxide anion radical). The disclosed compositions may target (e.g., bind to, inhibit formation of, or the like) one or more of these species, directly or indirectly.
The compositions provide several advantages over current technologies. In particular, the compositions can specifically target one or more species simultaneously, thereby providing reduced emissions and corrosion rates. The compositions can allow for specific components of the composition to focus on an intended target (e.g., mercury) without interference from another chemical species (e.g., manganese).
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present document, including definitions, will control. Preferred methods and materials are described below, although methods and materials similar or equivalent to those described herein can be used in practice or testing of the present invention. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.
As used in the specification and the appended claims, the singular forms “a,” “and” and “the” include plural references unless the context clearly dictates otherwise. The terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that do not preclude the possibility of additional acts or structures. The present disclosure also contemplates other embodiments “comprising,” “consisting of” and “consisting essentially of,” the embodiments or elements presented herein, whether explicitly set forth or not.
The term “mercury re-emission,” as used herein, refers to the phenomenon when water-soluble oxidized mercury (Hg2+) undergoes chemical reduction to water-insoluble elemental mercury (Hg0) in a wet flue gas desulfurization (WFGD) scrubber. It is believed the reduction occurs because of a reaction between mercury ions and sulfite ions present in the WFGD liquor. Because elemental mercury is insoluble in water, it exits the scrubber in the gas-phase. Thus the elemental mercury concentration in the flue gas exiting the scrubber is higher than the elemental mercury concentration entering the scrubber.
The term “percent mercury re-emission,” as used herein, refers to:
where “outlet” refers to EGU stack gas mercury measurement, “inlet” refers to gas concentrations at the inlet to the WFGD, “0” refers to the concentration of elemental mercury in the gas, and “T” refers to the total concentration of mercury in the gas. The “outlet” measurement may refer to mercury gas measurements made at any location after the gas has exited the WFGD.
The term “percent mercury oxidation,” as used herein, refers to:
where the super- and sub-scripts have the same meaning as defined in Equation A above.
The term “percent mercury capture,” as used herein, refers to:
where the super- and sub-scripts have the same meaning as defined in Equation A above.
The term “oxidation-reduction potential,” as used herein, refers to the summation of all the oxidation and reduction potentials in a given solution or scrubber liquor. As such, the oxidation-reduction potential varies depending on a liquor composition. Oxidation-reduction potential also depends on the fuel source of the electric generating unit, and operations of the wet flue gas desulfurizer (e.g., forced oxidation or natural, alkali source, purge rate).
The term “sulfite,” as used herein, refers to SO32−, and may have the structure shown below.
The term “sulfite radical,” as used herein, refers to SO3.−, and may have the structure shown below.
The term “sulfate,” as used herein, refers to SO42−, and may have the structure shown below.
The term “sulfate radical,” as used herein, refers to SO4.−, and may have the structure shown below.
The term “peroxymonosulfate radical,” as used herein, refers to SO5.−, and may have the structure shown below.
The term “persulfate,” as used herein, refers to S2O82−, and may have the structure shown below.
The term “carbon dioxide,” as used herein, refers to CO2, and may have the structure shown below.
The term “carbon dioxide anion radical,” as used herein, refers to CO2.−, and may have the structure shown below.
WFGD scrubber liquors contain multiple chemical species intended to react or interact with hazardous pollutants in order to prevent emission of the pollutants into the atmosphere. Within the liquor, a multitude of chemical reactions occur (e.g., oxidation/reductions), producing a variety of chemical species. Some of the reactions are favorable for reducing emissions, whereas others may result in mercury re-emission and/or corrosion, for example.
It has been discovered that several of these chemical species in a combustion gas and/or in a scrubber liquor can be targeted, directly or indirectly, to reduce mercury re-emissions and/or corrosion processes. In particular, persulfate species, transition metal species, and free radical species can be targeted to control mercury re-emission and/or corrosion processes.
In addition, various mercury species can be directly targeted to reduce mercury re-emission, such as those shown in Scheme 1. Other chemical species that may be present and can optionally be targeted include, but are not limited to, chloride, bromide, fluoride, HSO3−, CaSO4, SeO32−, organic acids, Mn2+, Fe3+, and other species.
a. Persulfate Species
Persulfate species present in WFGD scrubber liquors may be responsible for mercury re-emission. Persulfate species may also contribute to corrosion of scrubber equipment by increasing scrubber liquor oxidation-reduction potential, which leads to transition metal precipitation onto scrubber surfaces and galvanic corrosion.
Persulfate species (S2O82−) formation can be targeted to reduce mercury re-emissions and/or corrosion processes. In particular, constituents that lead to persulfate formation in WFGD scrubber liquors can be targeted to prevent formation of persulfate. The downstream activity of persulfate and species resulting from persulfate reaction, can also be targeted to reduce mercury re-emissions and/or corrosion processes. In particular, free radical species resulting from persulfate activity can be targeted to reduce mercury re-emissions and/or corrosion processes.
Persulfate species may cause mercury re-emission by initiating the reduction of ionic mercury species in the WFGD by oxidizing an organic acid (equation 1, dibasic acid (DBA) is shown as an example), which in turn yields CO2 anion radical (equation 2), which reduces mercuric chloride, leading to mercury re-emission (equation 3).
S2O82−→2SO4−. (1)
SO4−.+C2O42−(DBA)→SO42−+CO2−.+CO2 (2)
CO2−.+Hg2+→CO2+Hg+ (3)
The persulfate species may be formed in the WFGD via catalytic reaction of sulfite species over Mn and/or Fe solid surfaces, especially at high redox potential over 400 mV.
The reaction may be initiated by the transfer of an electron from a sulfite to a transition metal, such as iron or manganese, which are both in the +3 oxidation state. The reaction yields a sulfite anion radical (equation 4).
M3++SO32−→M2++SO3−. (4)
Reaction of the sulfite anion radical with oxygen produces peroxymonosulfate radical, which in turn reacts with another sulfite anion radical to produce persulfate (equations 5 and 6).
O2+SO3.−→SO5.− (5)
SO5.−+→SO3.−→S2O82− (6)
While chloride species in the scrubber liquor act as scavengers for persulfate, the chlorine resulting from this scavenging can catalyze propagation reactions resulting in more sulfate radicals (equation 7), which may contribute to further persulfate production and mercury re-emission.
S2O82−+2Cl−→2SO42−+Cl2 (7)
The oxidation of organics referred to above may also be responsible for releasing complexed mercury into the WFGD liquor, thus contributing to higher mercury re-emission.
b. Manganese Species (Mn4+ and Mn2+)
Manganese species, solid manganese species in particular, can contribute to mercury re-emission by catalyzing the formation of persulfate, which as described above, can lead to the reduction of ionic mercury to elemental mercury. Manganese species can also lead to corrosion of scrubber surfaces. Mn4+ species can cause corrosion by precipitating out of WFGD scrubber liquors onto surfaces of the scrubber and acting as galvanic cathodes (e.g., MnO2 deposits on WFGD alloys can act as galvanic cathodes to promote corrosion of the WFGD metal). These precipitated species can also catalyze the formation of persulfate (equation 4).
Manganese species can be targeted to reduce mercury re-emissions and/or corrosion processes. Manganese species that can be targeted include Mn4+ species and Mn2+ species. Mn4+ species can be targeted by controlling the scrubber oxidation-reduction potential. Oxidation-reduction potential (ORP) has an influence on mercury re-emission and corrosion in combustion processes due to its strong influence on transition metal oxidation state within WFGD scrubber liquors. At high ORP, manganese may be in the Mn4+ state and can precipitate out of the scrubber liquor onto WFGD surfaces, which leads to corrosion.
When ORP is lowered, the manganese may be reduced to Mn2+ and become soluble in the scrubber liquor.
The soluble Mn2+ can be optionally be targeted for removal from the scrubber liquor, eliminating the possibility of oxidation back to Mn4+ and its catalysis of persulfate formation. For example, both Mn4+ and Mn2+ can be targeted with binding agents to inactivate the metal surfaces for reaction. Such binding may prevent the reaction of the metals with sulfite, or engaging in other reactions that may contribute directly or indirectly to mercury re-emission and/or corrosion.
Targeting of persulfate species, as described above, can also be effective to reduce corrosion and/or mercury re-emission linked to Mn4+ activity. For example, when Mn-caused corrosion takes place, a strong oxidizer such as persulfate may be present. The oxidizer can raise the oxidation-potential of the scrubber liquor and precipitate out more manganese onto WFGD surfaces, leading to further corrosion. By reducing or preventing persulfate formation, the oxidation-reduction potential can be lowered, which results in less solid manganese precipitation and corrosion.
c. Free Radical Species
Free radical species can be targeted to reduce mercury re-emissions and/or corrosion processes. Free radical species that can be targeted include sulfite anion radicals, peroxymonosulfate radicals, and carbon dioxide anion radicals. The free radical species may be involved in the production of persulfate, as well as subsequent reactions leading to reduction of ionic mercury to elemental mercury. As shown in equations 4-6, sulfite anion radicals and peroxymonosulfate radicals may contribute to the formation of persulfate species in WFGD scrubber liquors. Equation 3 shows that carbon dioxide anion radical may contribute to mercury re-emission by reducing mercury species in WFGD scrubber liquors. Consequently, a multitude of free radicals can be targeted.
d. Mercury Species
Mercury species can be directly targeted to reduce mercury re-emissions. Mercury species that can be targeted include elemental mercury and ionic mercury species. Ionic mercury can be targeted for removal from WFGD scrubber liquors, thereby minimizing the species available for participation in mercury re-emission processes.
Based on the foregoing targets for reducing mercury re-emission and/or corrosion, compositions and methods are provided for targeting one or more of these species. The compositions and methods can include multiple components to target multiple species that contribute to mercury re-emission and/or corrosion processes. The compositions and methods can include components that enhance the effectiveness of other components, and in particular, effectiveness at targeting a specific chemical species. The composition and method components may together exhibit a synergistic effect.
In certain embodiments, a composition or method of the invention may target persulfate in a WFGD scrubber liquor. Targeting persulfate may prevent or reduce mercury re-emission (equations 1-3). For example, a composition or method can target species that result in persulfate formation, or species resulting from persulfate activity leading to mercury re-emission. Targeting persulfate may also allow for control of scrubber liquor oxidation-reduction potential. In particular, reduction of the ORP may mitigate precipitation of manganese species and their corrosive effect.
In certain embodiments, a composition or method of the invention may target transition metal species, including precipitated transition metal species (e.g., Mn4+). The composition may directly target transition metal species, or indirectly target said species by reducing oxidation-reduction potential of a WFGD scrubber liquor. The liquor, having a reduced ORP, may solubilize solid manganese, preventing its participation in corrosion of scrubber surfaces. Solubilizing the manganese may also prevent or minimize its reaction with sulfite, which would lead to persulfate formation (equation 4). The solubilized manganese can optionally be targeted by a composition or method of the invention, removing the manganese or inactivating the species in the scrubber liquor. The composition may bind to or flocculate the metal species to remove or inactivate it from the scrubber liquor. As such, the removed or inactivated metal will no longer be available to participate in corrosive processes and promotion of mercury re-emission. In certain embodiments, a composition or method of the invention can target mercury species, and in particular, can flocculate, chelate, or otherwise bind to ionic mercury species to prevent reduction of the mercury to elemental mercury.
In certain embodiments, a composition or method of the invention may target free radical species (e.g., SO3.−, SO5.−, CO2.−). The composition or method may prevent or reduce free radical participation in processes leading to mercury re-emission (equations 1-3), and/or persulfate formation (equations 5 and 6). The composition or method may specifically target carbon dioxide anion radical to prevent its reaction with ionic mercury, which would lead to elemental mercury and re-emission.
In certain embodiments, a composition or method of the invention can target two or more of: persulfate species, transition metal species (Mn, Fe, Hg), free radical species, and oxidation-reduction potential.
Suitable approaches for reducing mercury re-emission and/or controlling corrosion thus include:
(1) reducing the availability of metal species that can react with sulfite to produce persulfate (equation 4) by binding to or otherwise inactivating solid and/or solubilized metal species from further reactions (e.g., reduction of mercury to elemental mercury; reduction of sulfite to sulfite anion radical);
(2) reducing or preventing persulfate formation in the WFGD before it leads to mercury re-emission (equations 4-6);
(3) reducing or preventing persulfate initiated mercury re-emission by targeting downstream free radicals, such as carbon dioxide anion radical, which can react with and reduce ionic mercury (equation 3); and
(4) controlling the oxidation-reduction potential of WFGD scrubber liquors in order to reduce the amount of solid Mn/Fe deposited on scrubber surfaces.
In one aspect, disclosed are compositions for controlling mercury emissions from a scrubber process and/or reducing corrosion of scrubber equipment. The compositions may include at least two components selected from a mercury re-emission additive, a free radical scavenger, and a polymer dispersant. In certain embodiments, the compositions comprise a mercury re-emission additive and a free radical scavenger. In certain embodiments, the compositions comprise a mercury re-emission additive and a polymer dispersant. In certain embodiments, the compositions comprise a free radical scavenger and a polymer dispersant. In certain embodiments, the compositions comprise a mercury re-emission additive, a free radical scavenger, and a polymer dispersant.
The compositions may reduce mercury emissions and/or corrosion by one or more of the following: reducing the availability of solid metal species (e.g., Mn4+) that can react with sulfite leading to persurfate formation; reducing the amount of persulfate (S2O82) species present in a WFGD scrubber liquor; reducing the amount of free radical species (e.g., carbon dioxide anion radical) present in a WFGD scrubber liquor; and/or controlling the oxidation-reduction potential of WFGD scrubber liquors in order to reduce the amount of solid Mn/Fe deposited on scrubber surfaces.
One or more components of the disclosed compositions may bind to soluble mercury species and/or manganese species, thereby reducing mercury re-emission and/or corrosion of equipment used in the combustion process (e.g., a WFGD surface). In certain embodiments, the mercury re-emission additive and/or the polymer dispersant may bind to mercury species and/or manganese species. In certain embodiments, the composition includes a mercury re-emission additive configured to bind mercury species; and a polymer dispersant configured to bind manganese species.
The mercury re-emission additive may have a heavy metal selectivity of: Hg>Ag>Cd>Cu>Pb>Zn>Co(II)>Ni>Fe(II)>Mn. However, the manganese concentration in a scrubber liquor may be so high that it diminishes the effectiveness of a mercury re-emission additive, applied alone, to interact with and reduce emission of mercury species. A composition may include one component tailored to mercury (e.g., a mercury re-emission additive) and one component tailored to manganese (e.g., a polymer dispersant). The components may provide a synergistic effect for reducing mercury re-emission and/or corrosion.
One or more components of the composition may reduce the oxidation-reduction potential of a scrubber liquor, thereby increasing soluble manganese species (e.g., Mn2+) present in the scrubber liquor compared to insoluble manganese species (e.g., Mn4+). Optionally, the soluble manganese species can be targeted (e.g., via binding) by the same or another component of the composition. By solubilizing the manganese, and optionally binding it, the disclosed compositions may provide a reduction in manganese corrosion on alloy surfaces (e.g., a WFGD surface), as well as a reduction in the ability of solid manganese to react with sulfite to form sulfate anion radical, which leads to persulfate formation. In certain embodiments, the composition includes a mercury re-emission additive configured to reduce the oxidation-reduction potential of a scrubber liquor; and a polymer dispersant configured to bind solubilized manganese species present in the scrubber liquor.
One or more components of the composition may react with free radical species (e.g., carbon dioxide radical anion) to interrupt processes that lead to mercury re-emission and/or corrosion of metal surfaces. For example, a free radical scavenger may react with carbon dioxide anion radical before it reduces ionic mercury present in the scrubber liquor.
The dosage of the disclosed compositions may vary as necessitated to reduce or prevent mercury re-emission and/or to reduce or prevent corrosion. The dosage amounts can be selected based on, for example, a measured ionic mercury concentration and/or oxidation-reduction potential of a scrubber liquor. Process medium quality and extent of process medium treatment are a couple of factors that can be considered by one of ordinary skill in the art in selecting dosage amount. A jar test analysis is a typical example of what is utilized as a basis for determining the amount of dosage required to achieve effective metals removal in the context of a process water medium, e.g. wastewater. The dosage of the compositions may range from 1 to 10,000 ppm actives, or 100 to 1,000 ppm actives.
a. Mercury Re-Emission Additives
Mercury re-emission control additives that can be used with compositions of the invention include any additive suitable to reduce and/or prevent mercury re-emission from combustion processes, and in particular, scrubber liquors. In certain embodiments, the mercury re-emission additive may bind to or inactivate mercury. In certain embodiments, the mercury re-emission additive may be used to control scrubber liquor oxidation-reduction potential (e.g., reduce ORP). In certain embodiments, the mercury re-emission additive may be used to flocculate one or more metal species (e.g., mercury, iron, and/or manganese).
In certain embodiments, the mercury re-emission control additive may be a polymeric polydithiocarbamate compound (e.g., MerControl 8034, also referred to herein as “poly-DTC”), or another sulfur-containing additive such as sodium sulfide, sodium hydrosulfide, sodium bisulfide, or a polysulfide. In certain embodiments, the mercury re-emission additive may be a thiocarbonate or a polythiocarbonate. In certain embodiments, the mercury re-emission additive may be sodium polythiocarbonate.
In certain embodiments, the mercury re-emission control additive may be diethyldithiocarbamate or a sodium salt thereof. In certain embodiments, the mercury re-emission control additive may be dimethyldithiocarbamate or a sodium salt thereof.
In certain embodiments, the mercury re-emission control additive may be an inorganic polysulfide or blend, such as PRAVO, a product from Vosteen.
In certain embodiments, the mercury re-emission additive may be a sodium or calcium salt of 1,3,5-triazine-2,4,6(1H,3H,5H)-trithione (also referred to as trimercapto-S-triazine), such as TMT-15, a product from Degussa.
In certain embodiments, the mercury re-emission control additive may be an activated carbon, such as disclosed in U.S. Pat. No. 7,727,307 B2.
In certain embodiments, the mercury re-emission control additive may be a dithiol, a dithiolane, or a thiol having a single thiol group and either an oxygen or a hydroxyl group. Suitable dithiols include, but are not limited to, 2,3-dimercaptopropanol, dimercaptosuccinic acid, and 1,8-octanedithiol. Suitable dithiolanes include, but are not limited to, 1,2-dithiolane-3-valeric acid and 2-methyl 1,3-dithiolane. Suitable thiols include, but are not limited to, mercaptoacetic acid and sodium salts thereof.
In certain embodiments, the mercury re-emission control additive may be a halogen-containing compound. Suitable halogen-containing compounds include, but are not limited to, calcium bromide, sodium bromide, potassium bromide, hydrogen bromide, calcium iodide, and ammonium chloride.
In certain embodiments, a combination of mercury re-emission controlled additives may be used. In one preferred embodiment, the mercury re-emission control additive comprises a polymeric polydithiocarbamate compound.
(i) Ethylene Dichloride Ammonia Polymer Containing Dithiocarbamate Groups
The mercury re-emission control additive may be a water-soluble ethylene dichloride ammonia polymer having a molecular weight of from 500 to 10,000, and containing from 5 to 55 mole % of dithiocarbamate salt groups to prevent re-emission of mercury across a WFGD.
The polymer may be prepared by the reaction of ethylene dichloride and ammonia to provide a polyamine or polyimine. The polyamine or polyimine may have a molecular weight range of 500-100,000. In a preferred embodiment, the molecular weight may be 1,500 to 10,000, with the most preferred molecular weight range being 1,500 to 5,000.
The dithiocarbamate groups of the polymers may be introduced by the reaction of the polyamines or polyimines with carbon disulfide to produce polymeric dithiocarbamic acid or their salts. Such reaction is preferably carried out in a solvent such as water or alcohol at a temperature of from 30° C. and 100° C. for periods of time ranging between 1 and 10 hours. Good conversion may be obtained at temperatures between 40° and 70° C. for 2 to 5 hours.
The mole % of dithiocarbamate salt groups in the finished polymer may be within the range of 5 to 55%, 20 to 40 mole %, or 25 to 30 mole %. The salts include, but are not limited to, alkaline and alkali earth such as sodium, lithium, potassium or calcium.
The finished polymer may be applied to a combustion process at a ratio of 1:1 to 2000:1 weight copolymer to weight of mercury being captured. One preferred ratio may be from 5:1 to 1000:1 more preferably from 5:1 to 500:1.
(ii) Acrylic-x and Alkylamine Polymer
The mercury re-emission control additive may be a composition comprising a polymer derived from at least two monomers: acrylic-x and an alkylamine, wherein said acrylic-x has the following formula:
wherein X═OR, OH and salts thereof, or NHR2 and wherein R1 and R2 is H or an alkyl or aryl group, wherein R is an alkyl or aryl group, wherein the molecular weight of said polymer is between 500 to 200,000, and wherein said polymer is modified to contain a functional group capable of scavenging one or more compositions containing one or more metals.
The metals can include zero valent, monovalent, and multivalent metals. The metals may or may not be ligated by organic or inorganic compounds. Also, the metals can be radioactive and nonradioactive. Examples include, but are not limited to, transition metals and heavy metals. Specific metals can include, but are not limited to: copper, nickel, zinc, lead, mercury, cadmium, silver, iron, manganese, palladium, platinum, strontium, selenium, arsenic, cobalt and gold.
The molecular weight of the polymers can vary. For example, the target species/application for the polymers can be one consideration. Another factor can be monomer selection. Molecular weight can be calculated by various means known to those of ordinary skill in the art. For example, size exclusion chromatography, as discussed in the examples below can be utilized. When molecular weight is mentioned, it is referring to the molecular weight for the unmodified polymer, otherwise referred to as the polymer backbone. The functional groups that are added to the backbone are not part of the calculation. Thus the molecular weight of the polymer with the functional groups can far exceed the molecular weight range. In one embodiment, the molecular weight of the polymer is from 1,000 to 16,000. In another embodiment, the molecular weight of said polymer is from 1,500 to 8,000.
Various functional groups can be utilized for metal scavenging. The following phraseology would be well understood by one of ordinary skill in the art: wherein said polymer is modified to contain a functional group capable of scavenging one or more compositions containing one or more metals. More specifically, the polymer is modified to contain a functional group that can bind metals. In one embodiment, the functional group contains a sulfide containing chemistry. In another embodiment, the functional group is a dithiocarbamate salt group. In another embodiment, the functional groups are at least one of the following: alkylene phosphate groups, alkylene carboxylic acids and salts thereof, oxime groups, amidooxime groups, dithiocarbamic acids and salts thereof, hydroxamic acids, or nitrogen oxides.
The molar amounts of the functional group relative to the total amines contained in the unmodified polymer can vary as well. For example, the reaction of 3.0 molar equivalents of carbon disulfide to a 1.0:1.0 mole ratio acrylic acid/TEPA copolymer, which contains 4 molar equivalents of amines per repeat unit after polymerization, will result in a polymer that is modified to contain 75 mole % dithiocarbamate salt group. In other words, 75% of the total amines in the unmodified polymer have been converted to dithiocarbamate salt groups.
In one embodiment, the polymer may have between 5 to 100 mole % of the dithiocarbamate salt group. In a further embodiment, the polymer has from 25 to 90 mole % of the dithiocarbamate salt group. In yet a further embodiment, the polymer has from 55 to 80 mole % of the dithiocarbamate salt group.
Monomer selection will depend on the desired polymer. In one embodiment, the alkylamine is at least one of the following: an ethyleneamine, a polyethylenepolyamine, ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepetamine (TEPA) and pentaethylenehexamine (PEHA). In another embodiment, the acrylic-x is at least one of the following: methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate, propyl acrylate, and propyl methacrylate. In another embodiment, the acrylic-x is at least one of the following: acrylic acid and salts thereof, methacrylic acid and salts thereof, acrylamide, and methacrylamide.
The molar ratio between monomers that make up the polymer, especially acrylic-x and alkylamine can vary and depend upon the resultant polymer product that is desired. The molar ratio used is defined as the moles of acrylic-x divided by the moles of alkylamine. In one embodiment, the molar ratio between acrylic-x and alkylamine is from 0.85 to 1.5. In another embodiment, the molar ratio between acrylic-x and alkylamine is from 1.0 to 1.2. Various combinations of acrylic-x and alkylamines are encompassed by this invention as well as associated molecular weight of the polymers.
In one embodiment, the acrylic-x is an acrylic ester and the alkylamine is PEHA or TEPA or DETA or TETA or EDA. In a further embodiment, the molar ratio between acrylic-x and alkylamine is from 0.85 to 1.5. In yet a further embodiment, the molecular weight can encompass ranges: 500 to 200,000, 1,000 to 16,000, or 1,500 to 8,000. In yet a further embodiment, the acrylic ester can be at least one of the following: methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate, propyl acrylate, and propyl methacrylate, which is combined with at least one of the alklyamines, which includes PEHA or TEPA or DETA or TETA or EDA. In yet a further embodiment, the resulting polymer is modified to contain the following ranges of dithiocarbamate salt groups: 5 to 100 mole %, 25 to 90 mole %, or 55 to 80 mole %.
In another embodiment, the acrylic-x is an acrylic amide and the alkylamine is TEPA or DETA or TETA or EDA. In a further embodiment, the molar ratio between acrylic-x and alkylamine is from 0.85 to 1.5. In yet a further embodiment, the molecular weight can encompass ranges: 500 to 200,000, 1,000 to 16,000, or 1,500 to 8,000. In yet a further embodiment, the acrylic amide can be at least one or a combination of acrylamide and methacrylamide, which is combined with at least one of the alklyamines, which includes PEHA or TEPA or DETA or TETA or EDA. In yet a further embodiment, the resulting polymer is modified to contain the following ranges of dithiocarbamate salt groups: 5 to 100 mole %, 25 to 90 mole %, or 55 to 80 mole %.
In another embodiment, the acrylic-x is an acrylic acid and salts thereof and the alkylamine is PEHA or TEPA or DETA or TETA or EDA. In a further embodiment, the molar ratio between acrylic-x and alkylamine is from 0.85 to 1.5. In yet a further embodiment, the molecular weight can encompass ranges: 500 to 200,000, 1,000 to 16,000, or 1,500 to 8,000. In yet a further embodiment, the acrylic acid can be at least one or a combination of acrylic acid or salts thereof and methacrylic acid or salts thereof, which is combined with at least one of the alklyamines, which includes TEPA or DETA or TETA or EDA. In yet a further embodiment, the resulting polymer is modified to contain the following ranges of dithiocarbamate salt groups: 5 to 100 mole %, 25 to 90 mole %, or 55 to 80 mole %.
Additional monomers can be integrated into the polymer backbone made up of constituent monomers acrylic-x and alkylamine A condensation polymer reaction scheme can be utilized to make the basic polymer backbone chain. Various other synthesis methods can be utilized to functionalize the polymer with, for example, dithiocarbamate and/or other non-metal scavenging functional groups. One of ordinary skill in the art can functionalize the polymer without undue experimentation.
In certain embodiments, the composition can be formulated with other polymers such as a water soluble ethylene dichloride ammonia polymer having a molecular weight of from 500 to 100,000 which contains from 5 to 55 mole % of dithiocarbamate salt groups. In one embodiment, the molecular weight of the polymer is from 1,500 to 10,000 and contains 15 to 50 mole % of dithiocarbamate salt groups. In a preferred embodiment, the molecular weight of the polymer is from 1,500 to 5,000 and contains 30 to 55 mole % of dithiocarbamate salt groups.
In certain embodiments, the composition can be formulated with other small molecule sulfide precipitants such as sodium sulfide, sodium hydrosulfide, TMT-15® (sodium or calcium salts of trimercapto-S-triazine), dimethyldithiocarbamate, and/or diethyldithiocarbamate.
The mercury re-emission additives may be present in the composition in an amount of 0 wt % to 99 wt %, 20 wt % to 80 wt %, or 50 wt % to 60 wt %. The mercury re-emission additives may be present in the composition in an amount of about 10 wt %, about 20 wt %, about 30 wt %, about 40 wt %, about 50 wt %, about 60 wt %, about 70 wt %, about 80 wt %, or about 90 wt %. The mercury re-emission additive may be present in an amount of 50 wt %, 60 wt %, or 80 wt %.
b. Free Radical Scavengers
Free radical scavengers can be used to reduce mercury re-emission and/or corrosion. The free radical scavengers can be used to target free radical species that lead to persulfate formation (e.g., reduction of sulfite) or that lead to mercury re-emission (e.g., reduction of Hg2+).
Free radical scavengers that can be used in the compositions of the invention include, but are not limited to, substituted phenols (e.g., butylated hydroxytoluene, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol), derivatives of phenylenediamine (e.g., N,N′-di-2-butyl-1,4-phenylenediamine), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), citric acid, tertiary butylhydroquinone (TBHQ), tocopherols, ascorbic acid, glutathione, lipoic acid, uric acid, and enzymes (e.g., catalase, superoxide dismutase, various peroxidases, and the like).
The free radical scavenger may be present in the composition in an amount of 0 wt % to 99 wt %, 1 wt % to 30 wt %, 1 wt % to 25 wt %, 1 wt % to 20 wt %, or 1 wt % to 10 wt %. The free radical scavenger may be present in the composition in an amount of about 1 wt %, about 5 wt %, about 10 wt %, about 15 wt %, about 20 wt %, about 25 wt %, or about 30 wt %. The free radical scavenger may be present in the composition in an amount of 1 wt %, 10 wt %, 20 wt %, or 25 wt %.
c. Polymer Dispersants
Polymer dispersants can be used to reduce mercury re-emission and/or corrosion. The polymer dispersants can be used to target one or more transition metal species. The dispersants can be used to bind to or inactive mercury species, iron species, and/or manganese species (e.g., solubilized Mn2+).
The compositions disclosed herein may include a polymer dispersant. Suitable polymer dispersants include, but are not limited to, polyacrylic acid, polyacrylates, polymaleic acid, maleic anhydride/ethyl acrylate/vinyl acrylate terpolymer and alkyl epoxy carboxylate (abbreviated “AEC”), phosphinocarboxylic acids, such as phosphinosuccinate oligomers (abbreviated as “PSO”), and phosphonocarboxylic acids, such as phosphonocarboxylic (sulfonated) copolymer (abbreviated “POCA”, sold as Belclene 494).
The polymer dispersants may also be referred to herein as “binding agents.”
The polymer dispersant may be present in the composition in an amount of 0 wt % to 99 wt %, 10 wt % to 50 wt %, or 20 wt % to 40 wt %. The dispersant may be present in the composition in an amount of about 5 wt %, about 10 wt %, about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %, about 35 wt %, about 40 wt %, about 45 wt %, or about 50 wt %. The dispersant may be present in the composition in an amount of 10 wt %, 19 wt %, 20 wt %, 25 wt %, 40 wt %, or 50 wt %.
d. Dosage
In one embodiment, the amount of mercury re-emission control additive for effectively removing metals from contaminated waters may be within the range of 0.2 to 2 moles of dithiocarbamate per mole of metal, or 1 to 2 moles of dithiocarbamate per mole of metal contained in the water. According to one embodiment, the dosage of metal removal polymer required to chelate and precipitate 100 ml of 18 ppm soluble copper to about 1 ppm or less was 0.011 gm (11.0 mg) of polymer. The metal polymer complexes formed are self-flocculating and quickly settle. These flocculants are easily separated from the treated water.
In the context of applying the polymer to a gas system, such as a flue gas, the polymer can be dosed incrementally and capture rates for a particular metal, e.g. such as mercury, can be calculated by known techniques in the art. In certain embodiments, a mercury re-emission control additive, such as a water-soluble ethylene dichloride ammonia polymer with dithiocarbamate salt groups, may be applied to a scrubber liquor at a ratio of 1:1 to 2000:1 weight of polymer to weight of mercury being captured. One preferred dosage ratio is from 5:1 to 1000:1, more preferably from 5:1 to 500:1.
Methods of the present invention can be used in any process in which it is desirable to remove mercury from a flue gas and/or prevent or reduce corrosion of equipment used in combustion processes. For example, the methods of the present invention can be used in waste incineration plants (e.g., domestic waste, hazardous waste, or sewage sludge incineration plants), power stations (e.g., bituminous coal-fired, or lignite-fired power stations), other plants for high-temperature processes (e.g., cement burning), and high-temperature plants co-fired with waste or combined (multistage) high-temperature plants (e.g., power stations or cement rotary kilns having an upstream waste pyrrolysis or waste gasification.
Methods of the present invention can be used in processes of any dimension. The methods can be used in processes having a flue gas volumetric flow rate of 15×103 m3 S.T.P. db/h, for example for sewage sludge incineration, or of 50×103 m3 S.T.P. db/h, for example in hazardous waste incineration plants, or of 150×103 m3 S.T.P. db/h, for example in domestic waste incineration, and also in large power stations having, for example, 2-3×106 m3 S.T.P. db/h.
The methods can be used with any scrubbers currently used in the industry, including spray towers, jet bubblers, and co-current packed towers. These types of particulate control devices are provided as examples and are not meant to represent or suggest any limitation.
The compositions may be introduced into a scrubber and thereby into the scrubber liquor via several routes. For example, the compositions may be added to a virgin limestone or lime slurry prior to addition to a scrubber, to the recirculation loop of a scrubber liquor, or to a “low solids” return to a scrubber from the scrubber purge stream. The addition of the compositions can be made in any suitable location in a scrubber process, wholly or fractionally (i.e. a single feed point or multiple feed points), including but not limited to the make-up water for the lime or limestone slurry or the scrubber liquor.
In certain embodiments, the compositions may be added to a wet scrubber via a “low solids” liquor return. A portion of the liquor is usually continuously removed from the scrubber for the purpose of separating reaction byproducts from unused lime or limestone. One means of separation that is currently used is centrifugation. In this process the scrubber liquor is separated into a “high solids” and “low solids” stream. The high solids stream is diverted to wastewater processing. The low solids fraction returns to the wet scrubber and can be considered “reclaimed” dilute liquor. The compositions can conveniently be added to the reclaimed low solids stream prior to returning to the scrubber.
In certain embodiments, the compositions may be added to the wet scrubber via a “virgin liquor.” Virgin liquor is the water-based dispersion of either lime or limestone prior to exposure to flue gas and is used to add fresh lime or limestone while maintaining the scrubber liquor level and efficiency of the wet FGD. This is prepared by dispersing the lime or limestone in water. Here the composition can be added either to the dispersion water or the virgin liquor directly.
In certain embodiments, the compositions may be added to scrubber liquor injected directly into the flue gas prior to the scrubber for the purpose of controlling relative humidity of the flue gas or its temperature.
The scrubber liquors referred to herein may be water-based dispersions of calcium carbonate (limestone) or calcium oxide (lime) used in a wet Flue Gas Scrubber to capture SOx emissions. The liquor may also contain other additives such as magnesium and low-molecular weight organic acids, which function to improve the sulfur capture. One example of such an additive is a mixture of low-molecular weight organic acids known as dibasic acid (DBA). DBA consists of a blend of adipic, succinic, and glutaric acids. Each of these organic acids can also be used individually. In addition, another low-molecular weight organic acid that can be used to improve sulfur capture in a wet scrubber is formic acid. Finally, the scrubber liquor may also contain byproducts of the interaction between the lime or limestone and sulfur species, which leads to the presence of various amounts of calcium sulfite or calcium sulfate. The scrubber liquor may include the make-up liquor, return liquor, the reclaimed liquor, virgin liquor, and/or liquor injected directly into flue gasses.
The foregoing may be better understood by reference to the following examples, which are presented for purposes of illustration and are not intended to limit the scope of the invention.
It has been shown that as ORP is decreased in WFGD scrubber liquor, soluble Mn concentration increases (
The addition of persulfate to a scrubber liquor of a WFGD led to an increase in the amount of soluble mercury, which has been shown to result in mercury re-emission. This may be due to persulfate oxidizing organic matter, which agglomerate mercury species to larger particles (e.g., colloidal particles) and thus making it soluble, as shown in Table 2. Table 3 also shows the correlation between persulfate and soluble mercury levels, as well as ORP.
Correlating the soluble Mn concentration with mercury re-emission as well as with oxidation-reduction potential, relationships appear to be present (R2 values=˜0.72), as shown in
The addition of a Mn/Fe binding agent has the ability to blind the surface from sulfites, leading to a decrease in the transition metal's ability to convert sulfite to persulfate. As shown in Table 1, although the insoluble Fe and Mn levels are high at Day 1, mercury re-emission levels during this time (+/−2 hours) were very low. It can be inferred that the low mercury re-emission observed was due to the polymeric polydithiocarbamate mercury re-emission additive blinding the solid Mn and Fe surfaces, preventing persulfate formation.
The polymeric polydithiocarbamate mercury re-emission additive has however been shown to have a lower affinity for Mn and Fe over other cations (e.g., Hg2+). Other polymers, such as polyacrylate have higher affinities for Mn and Fe than the polymeric polydithiocarbamate mercury re-emission additive, and thus were investigated in their ability to bind to Mn and Fe within WFGD scrubber liquors. When adding polymeric polydithiocarbamate mercury re-emission additive or polyacrylate to a scrubber liquor containing persulfate, it was possible to significantly reduce the soluble mercury concentration, likely due to flocculation. The decrease in soluble mercury has been demonstrated to be accompanied by a significant drop in ORP value. A drop in ORP value has been demonstrated to lead to an increase in soluble Mn species. Indeed, when polymeric polydithiocarbamate mercury re-emission additive is added this phenomenon is observed, as shown in Table 4. However, with polyacrylate, no real increase in soluble Mn species is observed. It appears thus that polyacrylate indeed complexes the Mn species, leading to a low soluble Mn concentration. It can be envisaged that the same occurred on the solid Mn surfaces, deactivating them for catalytic activity in converting sulfites to persulfate.
The foregoing examples demonstrate that the compositions and methods may be used to reduce mercury re-emissions and/or control corrosion. Exemplary compositions of the invention may be prepared according to Table 5.
Any ranges given either in absolute terms or in approximate terms are intended to encompass both, and any definitions used herein are intended to be clarifying and not limiting. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, all ranges disclosed herein are to be understood to encompass any and all subranges (including all fractional and whole values) subsumed therein.
Furthermore, the invention encompasses any and all possible combinations of some or all of the various embodiments described herein. Any and all patents, patent applications, scientific papers, and other references cited in this application, as well as any references cited therein, are hereby incorporated by reference in their entirety.
This claims priority to U.S. Patent Application No. 61/729,823, filed on Nov. 26, 2012, U.S. Patent Application No. 61/729,828, filed on Nov. 26, 2012, and U.S. Patent Application No. 61/729,837, filed on Nov. 26, 2012, the contents of each of which are fully incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 61729823 | Nov 2012 | US | |
| 61729828 | Nov 2012 | US | |
| 61729837 | Nov 2012 | US |
