Patent Grant
11857942
Not applicable
Not applicable
Not applicable
Mercury is a known environmental hazard and leads to health problems for both humans and non-human animal species. Approximately 50 tons per year are released into the atmosphere in the United States, and a significant fraction of the release comes from emissions from coal burning facilities such as electric utilities. To safeguard the health of the public and to protect the environment, the utility industry is continuing to develop, test, and implement systems to reduce the level of mercury emissions from its plants. In the combustion of carbonaceous materials, it is desirable to have a process wherein mercury and other undesirable compounds are captured and retained after the combustion phase so that they are not released into the atmosphere.
One of the most promising solutions for mercury removal from flue gas is Activated Carbon Injection (ACI). Activated carbon is a highly porous, non-toxic, readily available material that has a high affinity for mercury vapor. This technology is already established for use with municipal incinerators. Although the ACI technology is effective for mercury removal, the short contact time between the activated carbon and the flue gas stream results in an inefficient use of the full adsorption capacity of the activated carbon. Mercury is adsorbed while the carbon is conveyed in the flue gas stream along with fly ash from the boiler. The carbon and fly ash are then removed by a particulate capture device such as an Electrostatic Precipitator (ESP) or baghouse.
Various embodiments are directed to a mercury adsorptive material comprising an adsorptive material having a volumetric iodine number of greater than 450 mg/cc based on the gravimetric iodine number determined using standard test method (ASTM) D-4607 or an equivalent thereof and the apparent density determined using (ASTM) D-2854 or an equivalent thereof. In some embodiments, the volumetric iodine number is about 500 mg/cc to about 650 mg/cc. The adsorptive material can be any material known in the art including, but not limited to activated carbon, reactivated carbon, graphite, graphene, carbon black, zeolite, silica, silica gel, clay, and combinations thereof. In some certain embodiments, the adsorptive material has a mean particle diameter (MPD) of about 1 μm to about 30 μm. In particular embodiments, the mercury adsorptive material may include one or more oxidizing agent, such as, but not limited to, chlorine, bromine, iodine, ammonium bromide, ammonium chloride, calcium hypochlorite, calcium hypobromite, calcium hypoiodite, calcium chloride, calcium bromide, calcium iodide, magnesium chloride, magnesium bromide, magnesium iodide, sodium chloride, sodium bromide, sodium iodide, potassium tri-chloride, potassium tri-bromide, potassium tri-iodide, and combinations thereof, and the one or more oxidizing agent may be about 5 wt. % to about 50 wt. % of a total adsorptive material. In certain embodiments, the mercury adsorptive material may include one or more nitrogen source such as, for example, ammonium containing compounds, ammonia containing compounds, amines containing compounds, amides containing compounds, imines containing compounds, quaternary ammonium containing compounds, and combinations thereof, and the one or more nitrogen source may be about 5 wt. % to about 50 wt. % of a total adsorptive material. In some embodiments, the one or more nitrogen source may be ammonium iodide, ammonium bromide, or ammonium chloride, amine halides, a quaternary ammonium halides, organo-halides, and combinations thereof. In further embodiments, the mercury adsorptive material may include an alkaline agent such as, but not limited to, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, sodium carbonate, sodium bicarbonate, trisodium hydrogendicarbonate dihydrate, and combinations thereof, and the alkaline agent may be provided at a concentration of greater than or equal to about 0.15 equivalents per 100 grams of absorptive material.
Other embodiments are directed to a system for removing mercury from flue gas including an adsorptive material having a volumetric iodine number of greater than 450 mg/cc based on the gravimetric iodine number determined using standard test method (ASTM) D-4607 or an equivalent thereof and the apparent density determined using (ASTM) D-2854 or an equivalent thereof. In some embodiments, the volumetric iodine number is about 500 mg/cc to about 650 mg/cc. The system can be any material known in the art including, but not limited to activated carbon, reactivated carbon, graphite, graphene, zeolite, silica, silica gel, clay, and combinations thereof. In some certain embodiments, the adsorptive material has a mean particle diameter (MPD) of about 1 μm to about 30 μm. In particular embodiments, the system may include one or more oxidizing agent, such as, but not limited to, chlorine, bromine, iodine, ammonium bromide, ammonium chloride, calcium hypochlorite, calcium hypobromite, calcium hypoiodite, calcium chloride, calcium bromide, calcium iodide, magnesium chloride, magnesium bromide, magnesium iodide, sodium chloride, sodium bromide, sodium iodide, potassium tri-chloride, potassium tri-bromide, potassium tri-iodide, and combinations thereof, and the one or more oxidizing agent may be about 5 wt. % to about 50 wt. % of a total adsorptive material. In certain embodiments, the system may include one or more nitrogen source such as, for example, ammonium containing compounds, ammonia containing compounds, amines containing compounds, amides containing compounds, imines containing compounds, quaternary ammonium containing compounds, and combinations thereof, and the one or more nitrogen source may be about 5 wt. % to about 50 wt. % of a total adsorptive material. In some embodiments, the one or more nitrogen source may be ammonium iodide, ammonium bromide, or ammonium chloride, amine halides, a quaternary ammonium halides, organo-halides, and combinations thereof. In further embodiments, the system may include an alkaline agent such as, but not limited to, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, sodium carbonate, sodium bicarbonate, trisodium hydrogendicarbonate dihydrate, and combinations thereof, and the alkaline agent may be provided at a concentration of greater than or equal to about 0.15 equivalents per 100 grams of absorptive material.
Further embodiments are directed to a method for mercury removal including the step of injecting an adsorptive material having a volumetric iodine number of greater than 450 mg/cc based on the gravimetric iodine number determined using standard test method (ASTM) D-4607 or an equivalent thereof and the apparent density determined using (ASTM) D-2854 or an equivalent thereof into a flue gas stream. In some embodiments, the adsorptive material may have a volumetric iodine number is about 500 mg/cc to about 650 mg/cc. The adsorptive material may be, for example, activated carbon, reactivated carbon, graphite, graphene, zeolite, silica, silica gel, clay, and combinations thereof and may have a mean particle diameter (MPD) of about 1 μm to about 30 μm. The adsorptive material may further include any of the additives described above.
In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. It will be readily understood that the aspects of the present disclosure, as generally described herein and illustrated in the Figures, can be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all of which are explicitly contemplated herein.
Before the present compositions and methods are described, it is to be understood that this invention is not limited to the particular processes, compositions, or methodologies described, as these may vary. It is also to be understood that the terminology used in the description is for the purpose of describing the particular versions or embodiments only, and is not intended to limit the scope of the present invention, which will be limited only by the appended claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, the preferred methods, devices, and materials are now described. All publications mentioned herein are incorporated by reference in their entirety. Nothing herein is to be construed as an admission that the invention is not entitled to antedate such disclosure by virtue of prior invention.
It must also be noted that as used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural reference unless the context clearly dictates otherwise. Thus, for example, reference to “a combustion chamber” is a reference to “one or more combustion chambers” and equivalents thereof known to those skilled in the art, and so forth.
As used herein, the term “about” means plus or minus 10% of the numerical value of the number with which it is being used. Therefore, about 50% means in the range of 45%-55%.
Embodiments of the invention are directed to mercury sorbents having enhanced mercury removal capabilities in flue gas streams. Such mercury sorbents have include a mercury adsorptive material having an iodine number of greater than 300 mg/g, and in other embodiments, the mercury adsorptive material may have an iodine number from about 700 mg/g to about 1500 mg/g. In still other embodiments, these mercury sorbents may include one or more additives that may further enhance the effectiveness of the mercury adsorptive material.
The mercury adsorptive material of the sorbent composition of various embodiments may include any material having an affinity for mercury. For example, in some embodiments, the mercury adsorptive material may be a porous sorbent having an affinity for mercury including, but not limited to, activated carbon, reactivated carbon, graphite, graphene, zeolite, silica, silica gel, clay, and combinations thereof, and in particular embodiments, the mercury adsorptive material may be activated carbon. The mercury adsorptive material may have any mean particle diameter (MPD). For example, in some embodiments, the MPD of the mercury adsorptive material may be from about 0.1 μm to about 100 μm, and in other embodiments, the MPD may be about 1 μm to about 30 μm. In still other embodiments, the MPD of the mercury adsorptive material may be less than about 15 μm, and in some particular embodiments, the MPD may be about 2 μm to about 10 μm, about 4 μm to about 8 μm, or about 5 μm or about 6 μm. In certain embodiments, the mercury adsorptive materials may have an MPD of less than about 12 μm, or in some embodiments, less than 7 μm, which may provide increased selectivity for mercury oxidation.
In certain embodiments, the mercury adsorbent may have high activity as determined by having an iodine number of greater than 300 mg/g. Iodine number is used to characterize the performance of adsorptive materials based on the adsorption of iodine from solution. This provides an indication of the pore volume of the adsorbent material. More specifically, iodine number is defined as the milligrams of iodine adsorbed by one gram of carbon when the iodine concentration in the residual filtrate is 0.02 normal. Greater amounts of adsorbed iodine indicates that the activated carbon has a higher surface area for adsorption and a higher degree of activation activity level. Thus, a higher “iodine number” indicates higher activity. As used herein, the term “iodine number” can refer to either a gravimetric iodine number or a volumetric iodine number. Gravimetric iodine number can be determined using standard test method (ASTM) D-4607, which is hereby incorporated by reference in its entirety, or equivalent thereof. Volumetric iodine number is a product of the gravimetric iodine number (mg of iodine adsorbed/gram of carbon) and the apparent density of the activated carbon (grams of carbon/cc of carbon), which an apparent density can be determined using ASTM D-2854, which is hereby incorporated by reference in its entirety, or an equivalent thereof. In other embodiments, granular or powdered carbon or any other form of carbon where the ASTM apparent density test cannot properly be applied, the apparent density can be determined using mercury porosimetry test ASTM 4284-12 to determine the void volume via mercury intrusion volume at 1 pound per square inch actual pressure. This intrusion volume defines the void volume of the carbon sample to allow calculation of the carbon particle density, and the apparent density is then calculated by correcting this particle density for the void fraction in a dense packed container of the carbon sample. The void fraction is 40% for a typical 3 fold range in particle size for the sample. Thus, Calculated Apparent Density (g.Carbon/cc.Carbon container)=Particle Density (g.carbon/cc.carbon particle volume)*(100%−40% voids)/100%. The result is a volume based activity with the units of mg of iodine adsorbed per cc of carbon.
Adsorbent materials typically used for mercury adsorption have an iodine number, based on the gravimetric iodine number, of about 300 mg/g to about 400 mg/g, which is thought to provide equivalent performance in mercury adsorption characteristics to adsorptive materials having higher iodine numbers. Various embodiments of the invention are directed to mercury sorbents that include adsorbent materials having gravimetric iodine number for greater than 400 mg/g, greater than 500 mg/g, greater than 600 mg/g, greater than 700 mg/g, greater than 800 mg/g, greater than 900 mg/g, and so on or any gravimetric iodine number therebetween. In other embodiments, the adsorptive material may have an iodine number of from about 500 mg/g to about 1500 mg/g, about 700 mg/g to about 1200 mg/g, or about 800 mg/g to about 1100 mg/g, or any gravimetric iodine number between these exemplary ranges. In further embodiments, mercury adsorbents exhibiting an iodine number within these exemplary ranges may be an activated carbon or carbonaceous char.
As determined using volumetric iodine number methods, adsorbent materials for mercury adsorption may have a volumetric iodine number from about 350 mg/cc to about 800 mg/cc. In embodiments of the invention described herein, the volumetric iodine number may be greater than 400 mg/cc, greater than 500 mg/cc, greater than 600 mg/cc, greater than 700 mg/cc, and so on or any volumetric iodine number therebetween. In other embodiments, the adsorptive material may have a volumetric iodine number of from about 350 mg/cc to about 650 mg/cc, about 400 mg/cc to about 600 mg/cc, about 500 mg/cc to about 600 mg/cc, about 500 mg/cc to about 700 mg/cc, or any volumetric iodine number between these ranges. In further embodiments, mercury adsorbents exhibiting an iodine number within these exemplary ranges may be an activated carbon or carbonaceous char, and in certain embodiments, these activated carbon or carbonaceous chars exhibiting a volumetric iodine number of 400 mg/cc or greater may be combined with activated carbons and carbonaceous chars exhibiting a volumetric iodine number that is less than 400 mg/cc.
Without wishing to be bound by theory, adsorbent materials having an iodine number within these exemplary ranges may provide improved adsorption over adsorbent materials having a gravimetric iodine number within the commonly used range of about 300 mg/g to about 400 mg/g. For example, in certain embodiments, about one half as much activated carbon having a gravimetric iodine number between about 700 mg/g to about 1200 mg/g or a volumetric iodine number of about 500 mg/cc to about 2200 mg/cc may be necessary to adsorb the amount of mercury adsorbed by conventional activated carbon. Thus, certain embodiments, are directed to methods in which about 5 lbs/hr to about 10 lbs/hr of activated carbon having an iodine number of from about 700 mg/g to about 1200 mg/g or a volumetric iodine number of about 500 mg/cc to about 2200 mg/cc can adsorb an equivalent amount of mercury as about 15 lbs/hr of an activated carbon having an gravimetric iodine number of about 500 mg/g (see, Example 1).
In still other embodiments, any of the adsorptive materials described above may be treated with one or more oxidizing agents that enhance mercury adsorption. For example, in some embodiments, the oxidizing agent may be a halogen salt including inorganic halogen salts, which for bromine may include bromides, bromates, and hypobromites, for iodine may include iodides, iodates, and hypoiodites, and for chlorine may be chlorides, chlorates, and hypochlorites. In certain embodiments, the inorganic halogen salt may be an alkali metal or an alkaline earth element containing halogen salt where the inorganic halogen salt is associated with an alkali metal such as lithium, sodium, and potassium or alkaline earth metal such as magnesium, and calcium counterion. Non-limiting examples of inorganic halogen salts including alkali metal and alkali earth metal counterions include calcium hypochlorite, calcium hypobromite, calcium hypoiodite, calcium chloride, calcium bromide, calcium iodide, magnesium chloride, magnesium bromide, magnesium iodide, sodium chloride, sodium bromide, sodium iodide, potassium tri-chloride, potassium tri-bromide, potassium tri-iodide, and the like. The oxidizing agents may be included in the composition at any concentration, and in some embodiments, no oxidizing agent may be included in the compositions embodied by the invention. In embodiments in which oxidizing agents are included, the amount of oxidizing agent may be from about 5 wt. % or greater, about 10 wt. % or greater, about 15 wt. % or greater, about 20 wt. % or greater, about 25 wt. % or greater, about 30 wt. % or greater, about 40 wt. % or greater of the total sorbent, or about 5 wt. % to about 50 wt. %, about 10 wt. % to about 40 wt. %, about 20 wt. % to about 30 wt. %, or any amount therebetween.
In further embodiments, any of the adsorptive materials described above may be treated with one or more nitrogen source. The nitrogen source of such agents may be any nitrogen sources are known in the art and can include, for example, ammonium, ammonia, amines, amides, imines, quaternary ammonium, and the like. In certain embodiments, the agent may be, for example, chlorine, bromine, iodine, ammonium halide, such as, ammonium iodide, ammonium bromide, or ammonium chloride, an amine halide, a quaternary ammonium halide, or an organo-halide and combinations thereof. In some embodiments, the nitrogen containing agent may be ammonium halide, amine halide, or quaternary ammonium halide, and in certain embodiments, the agent may be an ammonium halide such as ammonium bromide. In various embodiments, the nitrogen containing agent may be provided about 5 wt. % or greater, about 10 wt. % or greater, about 15 wt. % or greater, about 20 wt. % or greater, about 25 wt. % or greater, about 30 wt. % or greater, about 40 wt. % or greater of the total sorbent, or about 5 wt. % to about 50 wt. %, about 10 wt. % to about 40 wt. %, about 20 wt. % to about 30 wt. %, or any amount therebetween.
The ammonium halide, amine halide, or quaternary ammonium halide may be absent in some embodiments, in other embodiments, the ammonium halide, amine halide, or quaternary ammonium halide may be the only additive included in the sorbent composition, and in still other embodiments, the ammonium halide, amine halide, or quaternary ammonium halide may be combined with other agents such as, for example, halide salts, halide metal salts, alkaline agents, and the like to prepare a composition or sorbent encompassed by the invention. In particular embodiments, sorbent may include at least one of a halogen salt such as sodium bromide (NaBr), potassium bromide (KBr), or ammonium bromide (NH4Br).
In some embodiments, the adsorbent material may be combined with an acid gas suppression agent such as, for example, alkaline agent. Numerous alkaline agents are known in the art and currently used to remove sulfur oxide species from flue gas and any such alkaline agent may be used in the invention. For example, in various embodiments, the alkaline additive may be alkali oxides, alkaline earth oxides, hydroxides, carbonates, bicarbonates, phosphates, silicates, aluminates, and combinations thereof, and in certain embodiments, the alkaline agent may be calcium carbonate (CaCO3; limestone), calcium oxide (CaO; lime), calcium hydroxide (Ca(OH)2; slaked lime); magnesium carbonate (MgCO3; dolomite), magnesium hydroxide (Mg(OH)2), magnesium oxide (MgO), sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3), trisodium hydrogendicarbonate dihydrate (Na3H(CO3)2.2H2O; trona), and combinations thereof. In various embodiments, the alkaline agent may be provided at a concentration greater than or equal to about 0.15 equivalents per 100 grams of absorptive material, wherein one equivalent of the alkaline agent is defined as the amount required to produce one mole of hydroxyl ions or to react with one mole of hydrogen ions. In particular embodiments, such alkaline agents may have a relatively high surface area such as, for example, above 100 m2/g for neat materials. High surface area materials may provide improved kinetics and capabilities for acid gas or SOx mitigation while complementing halogen compounds and other added oxidants to provide oxidation of elemental mercury. Because alkaline agents are highly polar materials that may associate and bond with water, in various embodiments, alkaline agents may be combined with the primary mercury sorbent as a physical admixture and may not generally be present on the sorbent surface or contained within the sorbent pore structure.
In other embodiments, the mercury adsorptive material may be treated to enhance the hydrophobicity of the adsorptive materials with, for example, one or more hydrophobicity enhancement agents that impede the adsorption and transport of water or other treatments of the sorbent that achieve similar results. Embodiments are not limited to the type of treated mercury adsorptive material or the means by which the mercury adsorptive material has been treated with a hydrophobicity enhancement agent. For example, in some embodiments, the mercury adsorptive material may be treated with an amount of one or more elemental halogen that can form a permanent bond with the surface. The elemental halogen may be any halogen such as fluorine (F), chlorine (Cl), or bromine (Br), and in certain embodiments, the elemental halogen may be fluorine (F). In other embodiments, the mercury adsorptive material may be treated with a hydrophobicity enhancement agent such as a fluorine salt, organo-fluorine compound, or fluorinated polymer, such as, TEFLON®.
In such embodiments, treatment may be effectuated by grinding the mercury adsorptive material with the organo-fluorine compound or fluorinated polymer. In still other embodiments, carbon sorbents used as the mercury adsorptive material may be treated with mineral acids such as but not limited to, hydrochloric acid, nitric acid, boric acid, and sulfuric acid, under high temperature, e.g., greater than about 400° C. or greater than 600° C. or greater than 800° C. The concentration of the acid is not critical to such treatments and concentrations as low as 1.0 percent by weight or less may be used. Without wishing to be bound by theory, such treatment may enhance hydrophobicity and decreased activity for the catalytic oxidation of sulfur dioxide to sulfuric acid in the presence of oxygen and water. Evidence of such treatments can be found in a high contact pH and a reduced tendency for the carbon alone to decompose hydrogen peroxide when compared to the same carbon without such treatments.
The adsorbent material may be combined with an oxidizing agent, nitrogen containing compound, hydrophobicity agent, acid gas suppression agent, or other mercury removal agent (collectively, “additives”) in any way known in the art. For example, in some embodiments, the one or more additive may be introduced onto the surface of the adsorbent material by impregnation in which the adsorbent material is immersed in a liquid mixture of additives or the liquid mixture of additives is sprayed or otherwise applied to the adsorbent material. Such impregnation processes result in an adsorbent material in which the additives are dispersed on the surface of the adsorbent material.
In various other embodiments, treatment of the adsorbent material may be combined with one or more additive as a dry admixture in which particles of adsorbent are separated and apart from particles of additive having substantially the same size. For example, in some embodiments, may be provided by co-milling activated carbon with one or more additive to a mean particle diameter (MPD) of less than or equal to about 12 μm, less than or equal to about 10 μm, or less than about 7 μm. Without wishing to be bound by theory, reducing the mean particle diameter of the sorbent and additives by co-milling allows for a close localization of the sorbent and the additives, but the additives are not contained within the sorbent pore structure. These dry admixtures have been found to be surprisingly effective in facilitating rapid and selective mercury adsorption. This effect has been shown particularly effective when all of components of the sorbent are combined and co-milled or otherwise sized to a mean particle diameter of less than or equal to about 12 μm. Co-milling may be carried out by any means. For example, in various embodiments, the co-milling may be carried out using bowl mills, roller mills, ball mills, jet mills or other mills or any grinding device known to those skilled in the art for reducing the particle size of dry solids.
Although not wishing to be bound by theory, the small MPD may improve the selectivity of mercury adsorption as the halide effectively oxidizes the mercury. As such, dry admixtures of adsorbent materials and additive may allow for a higher percentage of active halide and alkaline agents to be included in the injected sorbent. Mercury adsorbents that are impregnated with an additive by treating with an aqueous solution of the additive, for example, commercial brominated carbon sorbents, especially those impregnated with elemental bromine, can only retain a small percentage of the additive on the surface of the adsorbent, and impregnation tends to clog the pores of porous mercury adsorbents reducing the surface area available for mercury adsorption. In contrast, the percentage of additive in a dry mixture may be greater than about 10 wt. %, greater than about 15 wt. %, greater than about 20 wt. %, or greater than about 30 wt. % and up to about 50 wt. %, up to about 60 wt. %, or up to about 70 wt. % without exhibiting a reduction in mercury adsorption efficiency.
While co-grinding is useful in some embodiments, adsorptive material and additives may be combined by any method. For example, in some embodiments, an adsorptive material and one or more additive may be combined by blending or mixing the materials into a single mercury sorbent that can then be injected into a flue gas stream. In other embodiments, combining may occur during use such that the adsorptive material and the one or more additive are held in different reservoirs and injected simultaneously into a flue gas stream.
Further embodiments are directed to methods for removing mercury from flue gas by injecting a mercury adsorbent including a mercury sorbent described above including an adsorbent material and one or more oxidizing agent, nitrogen containing compound, hydrophobicity agent, acid gas suppression agent, or other mercury removal agent into a flue gas stream. The sorbents described herein may be used to adsorb mercury in any flue gas stream. For example, the sorbents of various embodiments may be used in flue gas streams having no or extremely low SO3 content or flue gas streams containing high concentrations of other acid gases such as HCl, HF, or NOx species.
In some embodiments, the mercury adsorptive material and one or more additive may be combined prior to injection into the flue gas stream by, for example, mixing or blending, the mercury adsorptive material with the one or more additives. In other embodiments, the mercury adsorptive material and one or more additives may be injected separately into the flue gas stream and combined in the flue gas stream itself. In still other embodiments, the mercury adsorbent material and the one or more additives may be introduced into a flue gas stream in different portions of the flue gas stream. For example, in some embodiments, all adsorbent materials and additives may be introduced into the flue gas stream simultaneously and at the same portion of the flue gas stream. In other embodiments, an additive such as, for example, a halide salt may be introduced into a boiler or a upstream portion of the flue gas stream and the adsorbent and one or more additional additives may be introduced into the flue gas stream either simultaneously or separately in one or more downstream portions of the flue gas stream.
Although the present invention has been described in considerable detail with reference to certain preferred embodiments thereof, other versions are possible. Therefore the spirit and scope of the appended claims should not be limited to the description and the preferred versions contained within this specification. Various aspects of the present invention will be illustrated with reference to the following non-limiting examples.
Activated carbons of various activity levels were investigated for their ability to remove mercury from flue gas. Activity was based on the gravimetric iodine number (ASTM D-4607) and volumetric iodine number which the gravimetric iodine number converted to a volumetric basis using the density of the granular material (ASTM D2854). Carbons were all approximately 7 μm in size and were injected into test flue gas upstream of the electrostatic precipitator (ESP) either alone or in a dry admixture with 30% w/w ammonium bromide. Results are reported based on lbs/hr required to remove 90% of the mercury in the flue gas stream.
As illustrated in
This application is a divisional of U.S. application Ser. No. 15/368,900 entitled “Sorbents For Removal of Mercury” which was filed on Dec. 5, 2016 which is a continuation of U.S. application Ser. No. 13/841,315 entitled “Sorbents For Removal of Mercury” which was filed on Mar. 15, 2013 which claims priority to U.S. Provisional Application No. 61/658,258, entitled, “Sorbents for Removal of Mercury,” filed Jun. 11, 2012, each of which is incorporated herein by reference in its entirety.
| Number | Name | Date | Kind |
|---|---|---|---|
| 1984164 | Stock | Dec 1934 | A |
| 3194629 | Dreibelbis et al. | Jul 1965 | A |
| 3757488 | Austin et al. | Sep 1973 | A |
| 3961020 | Seki | Jun 1976 | A |
| 4174373 | Yoshida et al. | Nov 1979 | A |
| 4196173 | deJong et al. | Apr 1980 | A |
| 4215096 | Sinha et al. | Jul 1980 | A |
| 4331639 | Hass et al. | May 1982 | A |
| 4453978 | Okimura et al. | Jun 1984 | A |
| 4474896 | Chao | Oct 1984 | A |
| 4491609 | Degel et al. | Jan 1985 | A |
| 4500327 | Nishino et al. | Feb 1985 | A |
| 4708853 | Matviya et al. | Nov 1987 | A |
| 4828619 | Matsushita et al. | May 1989 | A |
| 5019162 | Suzuki et al. | May 1991 | A |
| 5064805 | Otowa | Nov 1991 | A |
| 5110362 | Hoarty et al. | May 1992 | A |
| 5187141 | Jha et al. | Feb 1993 | A |
| 5245106 | Cameron et al. | Sep 1993 | A |
| 5286292 | Tsukada et al. | Feb 1994 | A |
| 5322778 | Antrim et al. | Jun 1994 | A |
| 5336835 | McNamara | Aug 1994 | A |
| 5348755 | Roy | Sep 1994 | A |
| 5424077 | Lajoie | Jun 1995 | A |
| 5435980 | Felsvang et al. | Jul 1995 | A |
| 5654352 | MacDonald | Aug 1997 | A |
| 5658547 | Michalak et al. | Aug 1997 | A |
| 5695726 | Lerner | Dec 1997 | A |
| 5726118 | Ivey et al. | Mar 1998 | A |
| 6126910 | Wilhelm et al. | Oct 2000 | A |
| 6238641 | Hayden | May 2001 | B1 |
| 6284288 | Gubelmann et al. | Sep 2001 | B1 |
| 6514906 | Hayden | Feb 2003 | B1 |
| 6521037 | Hurt et al. | Feb 2003 | B1 |
| 6589318 | El-Shoubary et al. | Jul 2003 | B2 |
| 6638347 | El-Shoubary et al. | Oct 2003 | B2 |
| 6706111 | Young | Mar 2004 | B1 |
| 6719828 | Lovell et al. | Apr 2004 | B1 |
| 6783585 | Zacarias et al. | Aug 2004 | B2 |
| 6803025 | Meserole et al. | Oct 2004 | B2 |
| 6808692 | Oehr | Oct 2004 | B2 |
| 6818043 | Chang et al. | Nov 2004 | B1 |
| 6878358 | Vosteen et al. | Apr 2005 | B2 |
| 6890507 | Chen et al. | May 2005 | B2 |
| 6953494 | Nelson, Jr. | Oct 2005 | B2 |
| 6960329 | Sellakumar | Nov 2005 | B2 |
| 7273524 | Tomita et al. | Sep 2007 | B2 |
| 7404940 | Higgins et al. | Jul 2008 | B2 |
| 7435286 | Olson et al. | Oct 2008 | B2 |
| 7442352 | Lu et al. | Oct 2008 | B2 |
| 7514052 | Lissianski et al. | Apr 2009 | B2 |
| 7722843 | Srinivasachar | May 2010 | B1 |
| 8080088 | Srinivasachar | Dec 2011 | B1 |
| 8216535 | Pollack et al. | Jul 2012 | B2 |
| 8263524 | Skandan et al. | Sep 2012 | B1 |
| 8309046 | Pollack et al. | Nov 2012 | B2 |
| RE44124 | Lovell et al. | Apr 2013 | E |
| 8409330 | Pollack | Apr 2013 | B2 |
| 8450238 | Pollack et al. | May 2013 | B2 |
| 8551431 | Adams et al. | Oct 2013 | B1 |
| 8679430 | Pollack et al. | Mar 2014 | B2 |
| 8715599 | Pollack et al. | May 2014 | B2 |
| 8834606 | Pollack | Sep 2014 | B2 |
| 9068745 | Pollack et al. | Jun 2015 | B2 |
| 9308518 | Mimna et al. | Apr 2016 | B2 |
| 9321032 | Pollack et al. | Apr 2016 | B1 |
| 20010015359 | Benoist | Aug 2001 | A1 |
| 20030033930 | Tom et al. | Feb 2003 | A1 |
| 20030206843 | Nelson | Nov 2003 | A1 |
| 20040003716 | Nelson | Jan 2004 | A1 |
| 20040013589 | Vosteen et al. | Jan 2004 | A1 |
| 20040069186 | Zacarias et al. | Apr 2004 | A1 |
| 20040074391 | Durante et al. | Apr 2004 | A1 |
| 20040144287 | Tardif et al. | Jul 2004 | A1 |
| 20040200389 | Young | Oct 2004 | A1 |
| 20040206276 | Hill et al. | Oct 2004 | A1 |
| 20040220046 | Stockwell et al. | Nov 2004 | A1 |
| 20040244657 | Srinivasachar et al. | Dec 2004 | A1 |
| 20050019240 | Lu et al. | Jan 2005 | A1 |
| 20050039598 | Srinivasachar et al. | Feb 2005 | A1 |
| 20050147549 | Lissianski et al. | Jul 2005 | A1 |
| 20060048646 | Olson et al. | Mar 2006 | A1 |
| 20060051270 | Brunette | Mar 2006 | A1 |
| 20060090646 | Sawada et al. | May 2006 | A1 |
| 20060193763 | Cross et al. | Aug 2006 | A1 |
| 20060204418 | Chao et al. | Sep 2006 | A1 |
| 20060205592 | Chao et al. | Sep 2006 | A1 |
| 20060255494 | Ohtomo et al. | Nov 2006 | A1 |
| 20070041885 | Maziuk | Feb 2007 | A1 |
| 20070056479 | Gray | Mar 2007 | A1 |
| 20070056481 | Gray | Mar 2007 | A1 |
| 20070122327 | Yang et al. | May 2007 | A1 |
| 20070140941 | Comrie | Jun 2007 | A1 |
| 20070180990 | Downs et al. | Aug 2007 | A1 |
| 20070207923 | Lu et al. | Sep 2007 | A1 |
| 20070219404 | Matthews | Sep 2007 | A1 |
| 20070231230 | Meserole et al. | Oct 2007 | A1 |
| 20070234902 | Fair et al. | Oct 2007 | A1 |
| 20080116228 | Ryan et al. | May 2008 | A1 |
| 20080134888 | Chao et al. | Jun 2008 | A1 |
| 20080182747 | Sinha | Jul 2008 | A1 |
| 20080207443 | Gadkaree et al. | Aug 2008 | A1 |
| 20080219908 | Grochowski | Sep 2008 | A1 |
| 20080274874 | Heschel et al. | Nov 2008 | A1 |
| 20090007785 | Kimura et al. | Jan 2009 | A1 |
| 20090010828 | Holmes et al. | Jan 2009 | A1 |
| 20090056538 | Srinivasachar et al. | Mar 2009 | A1 |
| 20090081092 | Yang et al. | Mar 2009 | A1 |
| 20090136401 | Yang et al. | May 2009 | A1 |
| 20090235848 | Eiteneer et al. | Sep 2009 | A1 |
| 20100018395 | Srinivasachar et al. | Jan 2010 | A1 |
| 20100025302 | Sato et al. | Feb 2010 | A1 |
| 20100178624 | Srinivasachar | Jul 2010 | A1 |
| 20110048231 | Sinha | Mar 2011 | A1 |
| 20110076210 | Pollack et al. | Mar 2011 | A1 |
| 20110195003 | Durham et al. | Aug 2011 | A1 |
| 20110250110 | Keiser et al. | Oct 2011 | A1 |
| 20110250111 | Pollack et al. | Oct 2011 | A1 |
| 20110277846 | Brestovansky et al. | Nov 2011 | A1 |
| 20120085708 | Redding | Apr 2012 | A1 |
| 20120100053 | Durham et al. | Apr 2012 | A1 |
| 20120134903 | Brasseur et al. | May 2012 | A1 |
| 20120183458 | Olson et al. | Jul 2012 | A1 |
| 20120244355 | Pollack et al. | Sep 2012 | A1 |
| 20120263634 | Ergang et al. | Oct 2012 | A1 |
| 20130157845 | Nalepa et al. | Jun 2013 | A1 |
| 20130330257 | Tramposch | Dec 2013 | A1 |
| 20140205200 | Zeng | Jul 2014 | A1 |
| 20140224121 | Mimna et al. | Aug 2014 | A1 |
| 20150050202 | Filippelli et al. | Feb 2015 | A1 |
| 20160102019 | Pollack et al. | Apr 2016 | A1 |
| 20170056853 | Mimna et al. | Mar 2017 | A1 |
| 20170080402 | Tramposch et al. | Mar 2017 | A1 |
| Number | Date | Country |
|---|---|---|
| 2036746 | Feb 1992 | CA |
| 1388060 | Jan 2003 | CN |
| 104888713 | Sep 2015 | CN |
| 588531 | Nov 1933 | DE |
| 102007020422 | Oct 2008 | DE |
| 0289809 | Nov 1988 | EP |
| 2327921 | Jun 2011 | EP |
| 2858747 | Apr 2015 | EP |
| 1336241 | Nov 1973 | GB |
| 58020224 | Feb 1983 | JP |
| 61-118117 | Jun 1986 | JP |
| 62-213822 | Sep 1987 | JP |
| H-08178240 | Jul 1996 | JP |
| 2000038589 | Feb 2000 | JP |
| 2002331273 | Nov 2002 | JP |
| 2003038415 | Feb 2003 | JP |
| 2008240761 | Oct 2008 | JP |
| 4953591 | Jun 2012 | JP |
| 4953592 | Jun 2012 | JP |
| 2013-505832 | Feb 2013 | JP |
| 2013085360 | May 2013 | JP |
| 1993008902 | May 1993 | WO |
| 2000069991 | Nov 2000 | WO |
| 2001085307 | Nov 2001 | WO |
| 0393518 | Nov 2003 | WO |
| 2004089501 | Oct 2004 | WO |
| 2005092476 | Oct 2005 | WO |
| 2006039007 | Apr 2006 | WO |
| 2006101499 | Sep 2006 | WO |
| 2007112248 | Oct 2007 | WO |
| 2008064360 | May 2008 | WO |
| 2008143074 | Nov 2008 | WO |
| 2010042321 | Apr 2010 | WO |
| 2011127323 | Oct 2011 | WO |
| 2012030560 | Mar 2012 | WO |
| 2013063490 | May 2013 | WO |
| 2013188327 | Dec 2013 | WO |
| 2014082076 | May 2014 | WO |
| 2014126749 | Aug 2014 | WO |
| 2014205200 | Dec 2014 | WO |
| Entry |
|---|
| Anonymous: “Activated carbon—Wikipedia”, Aug. 7 Retrieved from the Internet: URL:https://en.wikipedia.org/wiki/Activated_carbon[retrieved on Aug. 7, 2018]. |
| European Patent Application No. 13804633.9 Office Action dated Aug. 13, 2018. |
| B-PAC TM High Performance Mercury Sorbent, Jan. 1, 2004, retrieved from internet May 16, 2014 at https://www.albemrnrk.com. |
| Supplementary European Search Report for coresponding European Application No. 13804633 dated Feb. 1, 2016. |
| Chinese Office Action for corresponding Chinese Application No. 201380042764.0 dated Jan. 21, 2016. |
| Supplementary European Search Report in corresponding European Application No. 1413604.7 dated Jan. 30, 2017. |
| International Search Report and Written Opinion dated Oct. 28, 2014 in corresponding International Patent Application No. PCT/US2014/043158. |
| Raposo et al., Mercury Speciation in Fluorescence Lamps by Thermal Release Analysis (2003), Waste Management 23(10):879-886. |
| International Search Report and Written Opinion for PCT/US2016/033556 dated Aug. 26, 2016. |
| Change et al., Mercury emission control technologies: An EPRI synopsis, Power Engineering, Nov. 1, 1995, vol. 99, Issue 11, Penwell Corporation, Tulsa, OK, U.S.A. (24 pages). |
| Office of Inspector General “Evaluation Report: Additional Analyses of Mercury Emissions Needed Before EPA Finalizes Rules for Coal-Fired Electric Utilities” Report No. 2005-P-00003, Feb. 3, 2005, pp. 1-54. |
| International Search Report and Written Opinion for PCT/US2016/044745 dated Oct. 14, 2016. |
| Third Official Office Action dated Aug. 20, 2018 issued for Mexican Patent Application No. MX/a/2014/014943. |
| Albemarle Corporation Website, “B-PAC.TM. High Performance Mercury Sorbent” Jan. 1, 2004, retrieved from internet May 16, 2014 https://www.albermarle.com. |
| Bittner et al., “Triboelectrostatic Fly Ash Beneficiation: An Update on Separation Technologies,” International Operations, pp. 1-69. |
| Campbell, et al., Mercury Control with Activated Carbon: Results from Plants with High SO.sub.3, Paper #08-A-174-Mega-AWMA, pp. 1-17; Proceedings from the2008 Power Plant Pollution Control “Mega” Symposium, Aug. 25-28, 2008, Baltimore, Maryland. |
| Colabella et al., “The Absorption and Subsequent Oxidation of AsH, and PH on Activated Carbon,” J. of Crystal Growth (Oct. 1988), 92(1-2):189-195. |
| Dombrowski, “Evaluation of Low Ash Impact Sorbent Injection Technologies at a Texas Lignite/PRB Fired Power Plant,” URS Corporation, pp. 1-27. |
| Feng et al., “Environmental Function Material,” Chemical Industry Press, p. 136 (translation). |
| Ghorishi et al., “An Experimental Study of Mercury Sorption by Activated Carbons and Calcium Hydroxide,” EPA Office of Research and Development, Air Pollution Prevention & Control Division, North Carolina pp. 1-17 (1998). |
| Gleiser et al., “Control of Mercury from MSW Combustors by Spray Dryer Absorption Systems and Activated Carbon Injection,” Proceedings of an International Specialty Conference, Williamsburg, Virginia, Mar. 1993, pp. 1-15. |
| Granite et al., “Novel Sorbents for Mercury Removal from Flue Gas,” Indus. & Engin. Chem. Res. (Apr. 2000), 39(4):1020-1029. |
| Hall et al., “Sorption of Phosphine by Activated Carbon Cloth and the Effects of Impregnation with Silver and Copper Nitrates and the Presence of Water” Carbon (1985), 23(4):353-371. |
| Hurt et al., “Strategies and Technology for Managing High-Carbon Ash” Brown University and University of Utah (Sep. 1, 2002-Feb. 28, 2003) pp. 1-13. |
| International Search Report and Written Opinion for PC T/US2014/014605 dated May 22, 2014. |
| International Search Report and Written Opinion for PCT/US2007/064579 dated Oct. 25, 2007. |
| International Search Report and Written Opinion for PCT/US2010050598 dated Jun. 27, 2011. |
| International Search Report and Written Opinion for PCT/US2011/031638 dated Dec. 28, 2011. |
| International Search Report and Written Opinion for PCT/US2013/045061 dated Oct. 11, 2013. |
| Japanese Office Action from counterpart application JP 2012-532246 dated Nov. 19, 2013. |
| Jarvis, et al., SO.sub.3 Removal as a Mercury Control Strategy: Reducing SO.sub.3 helps control mercury emissions and can boost plant efficiency and decrease operating costs, Power Industry Services (2008), 1-9. |
| Laflesh et al., “Progress Report on Mercury Control Retrofit at the Colstrip Power Station, Paper #91,” Aug. 30-Sep. 2, 2010, Presented at A&WMA's Power Plant Air Pollutant Control MEGA Symposium in Baltimore, MD, 1-23. |
| Laine et al., “Effect of the preparation method on the pore size distribution of activated carbon from coconut shell,” Carbon (1992), 30(4):601-604. |
| Lee et al., “Gas Phase Mercury Removal by Carbon-Based Sorbents,” Fuel Processing Tech. (2003), 84:197-206. |
| Li et al., “Mercury Emissions Control in Coal Combustion Systems Using Potassium Iodide: Bench-Scale and Pilot-Scale Studies,” Energy & Fuels (Jan. 5, 2009), 23:236-243. |
| Looney, et al., Activated Carbon Injection with SO.sub.3 Flue Gas Conditioning Test at Gulf Power's Mercury Research Center, Paper #78, pp. 1-7; Proceedings from the 2008 Power Plant Pollution Control “Mega” Symposium, Aug. 25-28, 2008, Baltimore, Maryland. |
| Lou et al. “Stability of Mercury on Three Activated Carbon Sorbents” Fuel Processing Tech. (2006), 87:679-685. |
| Macias-Perez, et al., SO.sub.2 retention on Cao/activated carbon sorbents. Part II: Effect of the activated carbon support, Fuel (Feb. 20, 2008), 87(12):2544-2550. |
| Mullett et al., “Removal of Elemental Mercury from Bayer Stack Gases Using Sulfur-Impregnated Activated Carbons,” Chem. Eng. J. (2012), pp. 133-142. |
| Muthu et al., “An Evaluation of Impregnated Respirator Canister Carbons for Phosphine Removal from Air,” Pestic. Sci. (1974), 5:245-249. |
| Nelson Jr. et al., “Accumulated Power-Plant Mercury-Removal Experience with Brominated PAC Injection Paper #95”, Aug. 30, 2004, Retrieved from Internet on May 15, 2014 at URL:http://www.netl.doe.gov/Filelibrary/Research/Coal/ewr/mercury/Mega2-4- 1990.pdf. |
| Office Action for corresponding Japanese Patent Application No. 2013-503964 dated May 27, 2014. |
| Paradis, “Impact of Mercury Sorbents on Fly Ash Use for Cement Replacement” Paper #164, URS Corporation, pp. 1-120. |
| Pollack, “Sorbent Injection: Taking the Technology from R&D to Commercial Launch,” Paper #188, Calgon Carbon Corporation, p. 1-24. |
| Presto, et al., Further Investigation of the Impact of Sulfur Oxides on Mercury Capture by Activated Carbon, Ind. Eng. Chem. Res. (Nov. 2, 2007), 46(24):8273-8276. |
| Presto, et al., Impact of Sulfur Oxides on Mercury Capture by Activated Carbon, Environ Sci. Technol. (Sep. 15, 2007), 41(18):6579-6584. |
| Sontheimer et al., “Evaluation Methods Utilizing Aqueous Solutions, in Activated Carbon for Water Treatment,” 1988, p. 100-103. |
| Strivastava et al., “Control of Mercury Emissions from Coal-Fired Electric Utility Boilers”, Mar. 1, 2006, Retrieved from Internet on May 15, 2014 at URL:http://pubs.acs.org/doi/pdf/10.1021/es062639u. |
| Strivastava, “Control of Mercury Emissions from Coal Fired Electric Utility Boilers: An Update,” Feb. 2010, Retrieved from Internet on May 16, 2014 at URL:http://nepis.epa.gov/Adobe/PDF/P1006LCB.pdf. |
| Supplementary European Search Report for corresponding European Patent Application No. 11 76 6760 dated May 21, 2014. |
| Supplementary European Search Report and Written Opinion for EP 10819662 dated Feb. 26, 2013. |
| Supplementary European Search Report and Written Opinion for EP 14751874 dated Sep. 12, 2016. |
| Supplementary European Search Report and Written Opinion for EP 13804633 dated Feb. 1, 2016. |
| U.S. Environmental Protection Agency, Case Study 11: Ash Fuel Reburn and Beneficiation at We Energies (Dec. 2003). |
| Uddin et al., “Rose of SO2 for Elemental Mercury Removal from Coal Combustion Flue Gas by Activated Carbon,” Energy & Fuels (2008), 22(4):2284-2289. |
| White et al. “Parametric Evaluation of Powdered Activated Carbon Injection for Control of Mercury Emissions from a Municipal Waste Combustor,” Paper No. 92-40.06, 1992 Annual Meeting, Air and Waste Management Association, Kansas City, Missouri, Jun. 1992. |
| Wirling, “Process Optimisation of Quasi-Dry Waste Gas Cleaning with Integrated Dioxin and Furan Adsorption,” (Sep. 2001) Presented at Pollutant Control Symposium—Solutions in Dioxin and Mercury Reduction, University of Alicante 1-13. |
| Wirling, “Sicherheitstechnische Aspekte bei der Anwendung von kohlenstoffhaltigen Sorbentien zur Flugstromadsorption,” (2006) Technik + Trends 126(6):47-54 (translated title—Safety Aspects in the Use of Carbonaceous Sorbents for Entrained-PhaseAdsorption). |
| Yan et al., “Bench-Scale Experimental Evaluation of Carbon Performance on Mercury Vapour Adsorption,” Fuel (2004), 83:2401-2409. |
| Boehm et al, Activation of Carbon Catalysts for Oxidation Reactions . . . , Journal de Chimie Physique, 84:1449-1455 (1987), Abstract. |
| Database WPI Week 197450, Dement Publications Ltd., London, GB: AN 1974-86197V, XP002454207. |
| Database WPI8 Week 197450, Derwent Publications Ltd., London, GB; AN 1974-86198V, XP002454206. |
| Wang et al. “An Appraisal of the Surface Chemistry and Catalytic Oxidative Activity of the Nitrogen-Modified Activated Carbon by XPS” Cuihva Xuebao, 10(4):357-364 (1989) (Abstract). |
| Product Bulletin for Calgon Carbon Corporation entitled “HGR® 4×10 for Mercury Removal, Granular Activated Carbon”, 2013 (1 page). |
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| 20200047155 A1 | Feb 2020 | US |
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