Mitigation of mercury vapor emissions

Abstract

To provide recovery of mercury removal efficiency and mitigation of mercury vapor emissions from a sorbent material.SOLUTION: Some aspects of the present disclosure relate to a method comprising obtaining a sorbent polymer composite material, contacting the sorbent polymer composite material with mercury vapor to form a used sorbent polymer composite material; wherein the used sorbent polymer composite material comprises oxidized mercury and wherein the used sorbent polymer composite material emits oxidized mercury vapor; and contacting the used sorbent polymer composite material with a halogen source, so as to result in a treated sorbent polymer composite material. In some embodiments, the treated sorbent polymer composite material emits less than 0.01 μg oxidized mercury vapor per minute per gram of the treated sorbent polymer composite, compared to a used sorbent polymer composite, when measured at 65°C in air having a relative humidity of 95%.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The field of this disclosure relates to restoring mercury removal efficiency from sorbent materials and reducing mercury vapor emissions. [Background technology]

[0002] Coal-fired power plants, municipal waste incinerators, and oil refineries produce large amounts of flue gas containing a wide variety of environmental pollutants. One such pollutant is mercury. Mercury is highly toxic and dangerous to the environment. As such, mercury emissions are subject to strict regulations. Therefore, improved methods for reducing mercury from flue gas streams are highly desirable.

[0003] One method for removing mercury from flue gas streams involves the use of sorbent materials, including activated carbon. Powdered activated carbon is typically injected into the flue gas stream before the electrostatic precipitator or fabric filter. While effective, this method often requires very large amounts of injected carbon to achieve low mercury levels. Powdered carbon injection is expensive and generates large amounts of mercury-containing waste, which can limit the value of the fly ash for use in cement or other applications. Fixed-bed processes, which utilize carbon more effectively than powder injection, are difficult to implement in environments containing these particles due to concerns about clogging. As a result, fixed-bed processes have generally been applied downstream of flue gas desulfurization (FGD) units. The cooled flue gas exiting the FGD is introduced into a sorbent, where mercury vapor is absorbed and removed. The flue gas is then discharged to the stack substantially free of mercury vapor.

[0004] Sorbent-polymer composites utilizing activated carbon-loaded PTFE with various additives to enhance mercury capture have proven particularly effective in fixed-bed mercury removal applications.

[0005] One drawback to high mercury removal efficiency over long periods of time is the depletion of capture promoter additives and the accumulation of oxidized mercury species. The depletion of capture promoter additives leads to a decrease in mercury removal efficiency, while the accumulation of oxidized mercury species can lead to mercury vapor emissions. Oxidized mercury species are ubiquitous in coal combustion flue gases. In particular, mercury halides, such as mercury(II) chloride, mercury(II) bromide, and mercury(II) iodide, have significantly higher vapor pressures and can emit vapors under certain conditions. Mercury halides can result from coal combustion, the use of bromine salts in coal, or as a by-product from the reaction of iodized activated carbon with mercury. In some instances, vapor pressure resulting from the accumulation of oxidized mercury species can cause vapor emissions, which reduces effective removal efficiency and imposes practical limits on the life of fixed-bed adsorbents.

[0006] Over time, oxidized mercury species can accumulate in and on the sorbent. This accumulation of oxidized mercury species can lead to vapor emissions. Mercury limits are generally set at 10 μg / m 3 The level is set at less than 10 μg / m 3 of mercury corresponds to approximately 1 ppb. As a result, very small amounts of oxidized mercury can produce measurable levels of mercury. The reduced removal efficiency and mercury vapor release can ultimately limit the ability of mercury sorbents to meet compliance goals. Thus, the accumulation of oxidized mercury can limit the lifespan of sorbents.

[0007] Therefore, there is a need for a method to reduce the vapor emissions of oxidized mercury from sorbents. Summary of the Invention

[0008] One aspect of the present disclosure is a method for manufacturing a semiconductor device comprising: obtaining an adsorbent-polymer composite material comprising an adsorbent material and a polymer material; upon contacting the sorbent polymer composite with mercury vapor to form a spent sorbent polymer composite, the spent sorbent polymer composite contains oxidized mercury, and the spent sorbent polymer composite releases oxidized mercury vapor; and Upon contacting the spent adsorbent polymer composite with a halogen source to obtain a treated adsorbent polymer composite, the treated adsorbent polymer composite releases 0.01 μg to 0.10 μg lower oxidized mercury vapor per minute per gram of treated adsorbent polymer composite compared to the spent adsorbent polymer composite when measured at 65° C. in air having 95% relative humidity. The present invention relates to a method characterized in that

[0009] In a further embodiment, the method further comprises repeating the step of contacting the spent sorbent polymer composite material with the halogen source until the treated sorbent polymer composite material releases less than 0.01 μg of mercury vapor per minute per gram of oxidized mercury when measured at 65° C. in air having 95% relative humidity.

[0010] In a further embodiment, the spent sorbent-polymer composite has a first mercury removal efficiency, the treated sorbent-polymer composite has a second mercury removal efficiency, and the second mercury removal efficiency is 10% to 100% greater than the first mercury removal efficiency.

[0011] In a further embodiment, the step of contacting the spent sorbent-polymer composite material with a halogen source is carried out until the treated sorbent-polymer composite material has a second mercury removal efficiency that is greater than two times the first mercury removal efficiency.

[0012] In a further embodiment, the treated adsorbent-polymer composite material comprises 0.1 wt % to 10 wt % of the halogen source, based on the weight of the treated adsorbent-polymer composite material.

[0013] In a further aspect, the method includes contacting the spent adsorbent polymer composite material with the halogen source until the treated adsorbent polymer composite material comprises between 1 wt. % and 5 wt. % of the halogen source, based on the weight of the treated adsorbent polymer composite material.

[0014] In further embodiments, the polymeric material is at least one of polytetrafluoroethylene (PTFE), polyfluoroethylenepropylene (PFEP), polyperfluoroacrylate (PPFA), polyvinylidene fluoride (PVDF), terpolymers of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride (THV), polychlorotrifluoroethylene (PCFE), and other copolymers or terpolymers comprising at least one fluoromonomer, with or without additional non-fluorinated monomers.

[0015] In a further embodiment, the adsorbent material is activated carbon.

[0016] In a further embodiment, the halogen source is an alkali metal halide, an ammonium halide, a quaternary ammonium halide, or a combination thereof.

[0017] In a further embodiment, the alkali metal halide is sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, or a combination thereof.

[0018] In a further embodiment, the quaternary ammonium halide is tetramethylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, ammonium chloride, ammonium bromide, or a combination thereof.

[0019] In a further aspect, the step of contacting the spent adsorbent polymer composite material with a halogen source comprises spraying the spent adsorbent polymer composite material with a solution comprising the halogen source.

[0020] In a further aspect, the step of contacting the spent adsorbent polymer composite material with a halogen source comprises immersing the spent adsorbent polymer composite material in a solution comprising the halogen source.

[0021] In a further embodiment, the solution comprises 0.01 wt % to 10 wt % of a halogen source based on the weight of the adsorbent-polymer composite material or the spent adsorbent-polymer composite material.

[0022] In a further embodiment, the solution is an aqueous solution.

[0023] In a further embodiment, the solution is a non-aqueous solution.

[0024] In a further embodiment, the non-aqueous solution comprises an alcohol.

[0025] In a further embodiment, the alcohol comprises one or more of methanol, ethanol, or isopropanol.

[0026] In a further embodiment, the solution further comprises a surfactant.

[0027] In a further embodiment, the solution comprises 0.001 wt% to 0.1 wt% surfactant based on the weight of the solution.

[0028] In a further embodiment, the surfactant is a non-ionic surfactant.

[0029] In a further embodiment, the solution comprises a co-solvent.

[0030] In a further embodiment, the solution comprises 10 wt% to 50 wt% of a co-solvent based on the weight of the solution.

[0031] In a further embodiment, the oxidized mercury comprises a mercury halide.

[0032] In a further embodiment, the treated sorbent-polymer composite material comprises a complex of (i) oxidized mercury and (ii) a halogen source.

[0033] Another aspect of the present disclosure is a method for manufacturing a semiconductor device comprising: adsorbent material, a polymeric material, and Chemical complexes containing oxidized mercury and a halogen source 1. A treated adsorbent-polymer composite material comprising: The treated sorbent polymer composite material releases 0.01 μg to 0.10 μg of oxidized mercury vapor per minute per gram of treated sorbent polymer composite material compared to a used sorbent polymer composite material when measured at 65° C. in air having 95% relative humidity; and The spent adsorbent polymer composite material comprises: the spent adsorbent-polymer composite material is free of halogen sources; and the oxidized mercury in the spent adsorbent polymer composite material is not in a complex with a halogen source; The present invention relates to a treated adsorbent-polymer composite material, characterized in that it is identical to the treated adsorbent-polymer composite material, except that:

[0034] In a further embodiment, the chemical complex has the formula HgX4 2- (Wherein, X is chloride (Cl - ), bromide (Br - ) or iodide (I - ) has).

[0035] In a further embodiment, the chemical complex has the formula HgX3 - (Wherein, X is chloride (Cl - ), bromide (Br - ) or iodide (I - ) has).

[0036] In a further embodiment, the chemical complex is integrated into the matrix of the treated adsorbent-polymer composite material. [Brief explanation of the drawings]

[0037] Several embodiments of the present disclosure are described herein, by way of example only, with reference to the accompanying drawings. Referring now specifically to the drawings in detail, it is emphasized that the illustrated embodiments are by way of example and for purposes of illustrative discussion of embodiments of the present disclosure. In this regard, the description taken together with the drawings will make apparent to those skilled in the art how embodiments of the present disclosure may be practiced.

[0038] [Figure 1] FIG. 1 shows the effect of the halogen source of the present disclosure on the removal efficiency of oxidized mercury from the sorbent-polymer composite material.

[0039] [Figure 2] FIG. 2 shows mercury release from the sorbent polymer composite before and after treatment with an exemplary halogen source.

[0040] [Figure 3] FIG. 3 shows mercury release from the sorbent polymer composite before and after treatment with another exemplary halogen source.

[0041] [Figure 4] Figure 4 shows the derivatives of the Hg L111 XANES spectra of HgI2, (Bu4N)HgI3, and field-exposed adsorbent polymer composite samples. DETAILED DESCRIPTION OF THE INVENTION

[0042] Among these disclosed benefits and improvements, other objects and advantages of the present disclosure will become apparent from the following description taken in conjunction with the accompanying drawings. Detailed embodiments of the present disclosure are disclosed herein. However, it should be understood that the disclosed embodiments are merely exemplary of the disclosure, which may be embodied in various forms. Furthermore, each of the examples provided for various embodiments of the present disclosure is intended to be illustrative and not limiting.

[0043] Throughout the specification and claims, the following terms have the meanings expressly associated therewith, unless the context clearly dictates otherwise. As used herein, the phrases "in one embodiment," "in an embodiment," and "in some embodiments" do not necessarily refer to the same embodiment, although they may be the same embodiment. Additionally, as used herein, the phrases "in another embodiment" and "in some other embodiments" do not necessarily refer to different embodiments, although they may be different embodiments. Thus, as described below, various embodiments of the present disclosure can be readily combined without departing from the scope or spirit of the present disclosure.

[0044] As used herein, the term "based on" is not exclusive and allows for based on additional factors not recited, unless the context clearly dictates otherwise. Furthermore, throughout this specification, the meanings of "a," "an," and "the" include plural references. The meaning of "in" includes "in" and "on."

[0045] In some embodiments, an adsorbent-polymer composite material is obtained. As used herein, an "adsorbent-polymer composite material" is defined as an adsorbent material embedded within a matrix of a polymeric material.

[0046] In some embodiments, the sorbent polymer composite material is contacted with mercury vapor, thereby resulting in a spent sorbent polymer composite material. As used herein, a "spent sorbent polymer composite material" is an sorbent polymer composite material that has been contacted with mercury vapor until the sorbent polymer composite material releases mercury vapor at a release rate of at least 0.01 μg of mercury vapor per minute per gram of sorbent polymer composite when measured at 65° C. in air having 95% relative humidity. In some embodiments, a "spent sorbent polymer composite material" is an sorbent polymer composite material that has been contacted with a flue gas stream containing mercury vapor until the sorbent polymer composite material releases mercury vapor at a release rate of at least 0.01 μg of mercury vapor per minute per gram of sorbent polymer composite when measured at 65° C. in air having 95% relative humidity. In some embodiments, the flue gas stream can contain additional components, such as, but not limited to, SO x and NO x In some embodiments, the mercury vapor in the flue gas stream comprises oxidized mercury, elemental mercury, or any combination thereof. In some embodiments, the spent sorbent-polymer composite material can be formed in a commercial-scale process. In some embodiments, the spent sorbent-polymer composite material can be made under laboratory conditions.

[0047] In some embodiments, the release rate may be converted to a release concentration, as described herein below. In some embodiments, the release rate of the spent adsorbent-polymer composite material is at least 1 μg / m when measured at 65° C. in air having 95% relative humidity. 3 In some embodiments, the release rate of the spent adsorbent-polymer composite material is at least 5 μg / m when measured at 65° C. in air having 95% relative humidity. 3 In some embodiments, the release rate of the spent adsorbent-polymer composite material is at least 10 μg / m when measured at 65° C. in air having 95% relative humidity. 3In some embodiments, the release rate of the spent adsorbent-polymer composite material corresponds to a release concentration of 1 μg / m when measured at 65° C. in air with 95% relative humidity. 3 ~10μg / m 3 In some embodiments, the release rate of the spent adsorbent-polymer composite material is greater than or equal to 5 μg / m when measured at 65° C. in air with 95% relative humidity. 3 ~10μg / m 3 corresponds to the emitted concentration of

[0048] In some embodiments, the spent sorbent polymer composite material contains oxidized mercury and releases oxidized mercury vapor, which may include at least one mercury halide, such as, but not limited to, HgCl, HgBr, HgI, or any combination thereof. The spent sorbent polymer composite material is contacted with a halogen source to form a treated sorbent polymer composite material.

[0049] As used herein, a "treated adsorbent polymer composite material" is defined as an adsorbent polymer composite material that was at one time a "used adsorbent polymer material" as defined herein, but that has then been contacted with a halogen source until the adsorbent polymer material releases mercury vapor at a release rate of less than 0.01 μg of mercury vapor per minute per gram of adsorbent polymer composite material when measured at 65° C. in air having 95% relative humidity.

[0050] In some embodiments, the spent sorbent polymer composite material is repeatedly contacted with a halogen source until the treated sorbent polymer composite material releases mercury vapor at a release rate of less than 0.01 μg of mercury vapor per minute per gram of sorbent polymer composite material when measured at 65° C. in air having 95% relative humidity. In some embodiments, the repeated contact with the halogen source is carried out until the treated sorbent polymer composite material releases mercury vapor at a release rate of less than 0.005 μg of mercury vapor per minute per gram of sorbent polymer composite material when measured at 65° C. in air having 95% relative humidity. In some embodiments, the repeated contact with the halogen source is carried out until the treated sorbent polymer composite material releases mercury vapor at a release rate of less than 0.001 μg of mercury vapor per minute per gram of sorbent polymer composite material when measured at 65° C. in air having 95% relative humidity.

[0051] In some embodiments, the repeated contact with the halogen source is carried out until the treated adsorbent polymer composite material releases mercury vapor at a release rate of 0.001 μg to 0.01 μg of mercury vapor per minute per gram of adsorbent polymer composite when measured at 65° C. in air having 95% relative humidity. In some embodiments, the repeated contact with the halogen source is carried out until the treated adsorbent polymer composite material releases mercury vapor at a release rate of 0.001 μg to 0.005 μg of mercury vapor per minute per gram of adsorbent polymer composite when measured at 65° C. in air having 95% relative humidity. In some embodiments, the repeated contact with the halogen source is carried out until the treated adsorbent polymer composite material releases mercury vapor at a release rate of 0.005 μg to 0.01 μg of mercury vapor per minute per gram of adsorbent polymer composite when measured at 65° C. in air having 95% relative humidity.

[0052] In some embodiments, the spent sorbent-polymer composite has a first mercury removal efficiency and the treated sorbent-polymer composite has a second mercury removal efficiency, hi some embodiments, the second mercury removal efficiency is greater than the first mercury removal efficiency.

[0053] In some embodiments, the spent sorbent polymer composite material is repeatedly contacted with the halogen source until the treated sorbent polymer composite material has a second mercury removal efficiency that is 10% to 50% higher than the first mercury removal efficiency. In some embodiments, the spent sorbent polymer composite material is repeatedly contacted with the halogen source until the treated sorbent polymer composite material has a second mercury removal efficiency that is 20% to 40% higher than the first mercury removal efficiency. In some embodiments, the spent sorbent polymer composite material is repeatedly contacted with the halogen source until the treated sorbent polymer composite material has a second mercury removal efficiency that is 25% to 35% higher than the first mercury removal efficiency.

[0054] In some embodiments, repeated contact with the halogen source is performed until the treated sorbent-polymer composite material has a second mercury removal efficiency that is 50% to 100% greater than the first mercury removal efficiency. In some embodiments, repeated contact with the halogen source is performed until the treated sorbent-polymer composite material has a second mercury removal efficiency that is 60% to 90% greater than the first mercury removal efficiency. In some embodiments, repeated contact with the halogen source is performed until the treated sorbent-polymer composite material has a second mercury removal efficiency that is 70% to 80% greater than the first mercury removal efficiency.

[0055] In some embodiments, repeated contacting is performed until the treated sorbent-polymer composite material has a second mercury removal efficiency that is more than 100% greater than the first mercury removal efficiency. In some embodiments, repeated contacting is performed until the treated sorbent-polymer composite material has a second mercury removal efficiency that is 200% or 500% greater than the first mercury removal efficiency. In some embodiments, repeated contacting is performed until the treated sorbent-polymer composite material has a second mercury removal efficiency that is 500% greater than the first mercury removal efficiency.

[0056] In some embodiments, the spent adsorbent polymer composite material is contacted with a halogen source to form a treated adsorbent polymer composite material, the treated adsorbent polymer composite material comprising 0.1% to 10% of the halogen source. In some embodiments, the spent adsorbent polymer composite material is contacted with a halogen source to form a treated adsorbent polymer composite material, the treated adsorbent polymer composite material comprising 0.5% to 5% of the halogen source. In some embodiments, the spent adsorbent polymer composite material is contacted with a halogen source to form a treated adsorbent polymer composite material, the treated adsorbent polymer composite material comprising 1% to 2% of the halogen source.

[0057] In some embodiments, the adsorbent-polymer composite material is repeatedly contacted with the halogen source until the treated adsorbent-polymer composite material contains 0.1% to 1.0% of the halogen source. In some embodiments, repeated contact with the halogen source is performed until the treated adsorbent-polymer composite material contains 0.2% to 0.8% of the halogen source. In some embodiments, repeated contact with the halogen source is performed until the treated adsorbent-polymer composite material contains 0.4% to 0.5% of the halogen source.

[0058] In some embodiments, repeated contact with the halogen source is performed until the treated adsorbent-polymer composite material contains 1% to 10% of the halogen source. In some embodiments, repeated contact with the halogen source is performed until the treated adsorbent-polymer composite material contains 2% to 8% of the halogen source. In some embodiments, repeated contact with the halogen source is performed until the treated adsorbent-polymer composite material contains 4% to 5% of the halogen source.

[0059] In some embodiments, the polymeric material of the adsorbent-polymer composite may comprise one or more homopolymers, copolymers, or terpolymers comprising at least one fluoromonomer with or without additional non-fluorinated monomers.

[0060] In some embodiments, the polymer material of the adsorbent-polymer composite can include at least one of polyfluoroethylene propylene (PFEP), polyperfluoroacrylate (PPFA), polyvinylidene fluoride (PVDF), terpolymers of tetrafluoroethylene, hexafluoropropylene or vinylidene fluoride (THV), and polychlorotrifluoroethylene (PCFE).

[0061] In some embodiments, the polymeric material of the adsorbent-polymer composite can include polytetrafluoroethylene (PTFE). In some embodiments, the polymeric material of the adsorbent-polymer composite can include expanded polytetrafluoroethylene (ePTFE).

[0062] In some embodiments, the adsorbent material of the adsorbent-polymer composite material comprises activated carbon. In some embodiments, the activated carbon material can be derived from one or more of coal, lignite, wood, coconut shells, or another carbonaceous material. In some embodiments, the adsorbent material can comprise silica gel or zeolite.

[0063] In some embodiments, the halogen source used to treat the spent sorbent-polymer composite material comprises one or more of an alkali metal halide, an ammonium halide, or a quaternary ammonium halide. The alkali metal halide can comprise one or more of sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, or potassium iodide. The quaternary ammonium halide can comprise one or more of tetramethylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, or tetrabutylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, ammonium chloride, ammonium bromide, or any combination thereof. In some embodiments, the halide comprises iodine.

[0064] In some embodiments, the addition of a halogen source, such as a halogen salt that complexes with oxidized mercury, can reduce vapor emissions from the spent sorbent material by lowering the vapor pressure of oxidized mercury.

[0065] In some embodiments, the oxidized mercury comprises one or more mercury halides. In some embodiments, the mercury halide is mercuric halide. In some embodiments, the mercury halide comprises one or more of mercury(II) chloride, mercury(II) bromide, or mercury(II) iodide. In some embodiments, the mercury halide is mercurous halide. In some embodiments, the mercurous halide comprises one or more of mercury(I) chloride, mercury(I) bromide, or mercury(I) iodide.

[0066] In some embodiments, the treated sorbent-polymer composite material comprises a complex of oxidized mercury and a halogen source.

[0067] In some embodiments, complexation of oxidized mercury can occur via one or both of the following reactions: (1) AX + HgX2 → AHgX3 and (2) AX + AHgX3 → A2HgX4, where A is one or more of an alkali metal, an ammonium cation, or a quaternary ammonium cation, and X is a halide.

[0068] In some embodiments, the treated adsorbent-polymer composite material can be formed by spraying a solution containing a halogen source onto the adsorbent-polymer composite material or a used adsorbent-polymer composite material. In some embodiments, the treated adsorbent-polymer composite material can be formed by immersing the adsorbent-polymer composite material or a used adsorbent-polymer composite material in a solution containing a halogen source. In some embodiments, the solution can include 0.01 wt% to 0.1 wt% of the halogen source, 0.1 wt% to 1 wt% of the halogen source, or 1 wt% to 10 wt% of the halogen source. In some embodiments, the solution can include 0.03 wt% to 0.06 wt% of the halogen source, 0.3 wt% to 0.6 wt% of the halogen source, or 3 wt% to 6 wt% of the halogen source. In some embodiments, the solution can include 0.04 wt% to 0.05 wt% of the halogen source, 0.4 wt% to 0.5 wt% of the halogen source, or 4 wt% to 5 wt% of the halogen source.

[0069] In some embodiments, the solution can be aqueous or non-aqueous. In some embodiments, the solution can include one or more cosolvents. In some embodiments, the solution can include 0.01 wt% to 1 wt% of one or more cosolvents, 1 wt% to 10 wt% of one or more cosolvents, or 10 wt% to 50 wt% of one or more cosolvents. In some embodiments, the solution can include 0.05 wt% to 0.5 wt% of one or more cosolvents, 2 wt% to 5 wt% of one or more cosolvents, or 20 wt% to 50 wt% of one or more cosolvents. In some embodiments, the solution can include 0.03 wt% to 0.25 wt% of one or more cosolvents, 3 wt% to 4 wt% of one or more cosolvents, or 30 wt% to 40 wt% of one or more cosolvents. In some embodiments, the solvent or cosolvent includes one or more alcohols, such as methanol, ethanol, or isopropanol. In some embodiments, no cosolvent is present.

[0070] In some embodiments, the solution used to form the treated adsorbent-polymer composite material can include one or more surfactants. In embodiments in which one or more surfactants are present, the solution can include a sufficient amount of surfactant to ensure that a critical micelle concentration is achieved. The critical micelle concentration is the concentration at which the surface tension of the solution does not decrease further with the addition of additional surfactant. In some embodiments, the solution can include 0.001 wt% to 0.01 wt% of one or more surfactants, or 0.01 wt% to 0.1 wt% of a surfactant. In some embodiments, the solution can include 0.005 wt% to 0.05 wt% of one or more surfactants, or 0.05 wt% to 0.5 wt% of one or more surfactants. In some embodiments, the solution can include 0.0075 wt% to 0.075 wt% of one or more surfactants, or 0.075 wt% to 0.75 wt% of a surfactant. In some embodiments, the one or more surfactants are one or more of a cationic, anionic, zwitterionic, or nonionic surfactant. In some embodiments, the one or more surfactants are non-ionic surfactants.

[0071] In some embodiments, the one or more surfactants can provide a surface tension of 1 to 30 dynes / cm. In some embodiments, the one or more surfactants can provide a surface tension of 5 to 20 dynes / cm. In some embodiments, the one or more surfactants can provide a surface tension of 10 to 15 dynes / cm.

[0072] In some embodiments, the one or more nonionic surfactants can include at least one of a secondary alcohol ethoxylate (e.g., DOW TERGITOL™ 15-S surfactant), an ethylene oxide-propylene oxide copolymer (e.g., DOW TERGITOL™ L surfactant), an octylphenol ethoxylate (e.g., the DOW TRITON X line of surfactants), a sorbitan monolaurate (e.g., CRODA SPAN™ 20), or a laurel amine oxide (e.g., STEPAN AMONYX® LO).

[0073] In some embodiments, the one or more cationic surfactants can include one or more long-chain quaternary amines (e.g., cetyltrimethylammonium bromide (CTAB)).

[0074] In some embodiments, the one or more anionic surfactants can include one or more perfluoroalkyl sulfonates (eg, perfluorooctyl sulfonate, PFOS).

[0075] Test Method An exemplary test for mercury vapor removal was conducted using an apparatus including: (1) an air supply regulated by a mass flow controller; (2) a mercury source generated by a small nitrogen purge of a DYNACALIBRATOR calibration gas generator (VICI Metronics, Inc., Poulsbo, WA, USA) containing a mercury permeation tube; (3) a sample cell fitted with a bypass and placed in an oven maintained at 65°C; (4) a stannous chloride / H2SO4 bubbler to convert oxidized mercury to elemental mercury; and (5) mercury detection with a RA915+ mercury analyzer (OHIO LUMEX Co., Inc., OH, USA) equipped with a short pathlength gas cell.

[0076] Mercury purification efficiency (η) is reported as the difference between the inlet mercury level (bypassing the sample) and the outlet level (passing the sample) divided by the inlet concentration.

[0077] η=(Inlet concentration - Outlet concentration) / (Inlet concentration)

[0078] Mercury Release Test Procedure Weighed samples (typically 10 mm x 150 mm) were tested for oxidized mercury release on a 1 cm x 1 cm glass square contained within an oven maintained at 65°C. The samples were exposed to flowing mercury-free air controlled by a mass flow controller. A membrane-based permeation device (Permapure) placed upstream of the sample nearly saturated the air stream with moisture. Total flow rates of 1 to 10 slpm (standard liters per minute) were used, depending on the required sensitivity. Air exiting the sample passed through a tin(II) chloride / sulfuric acid trap to convert oxidized mercury to elemental mercury. A heated PFA sample line was used between the oven and the tin(II) chloride / sulfuric acid trap to prevent condensation of mercury halides. The outlet mercury concentration was measured with an RA915+ mercury analyzer (OHIO LUMEX) using a short-pathlength cell. The release rate was calculated based on the following equation:

[0079] Release rate (μgHg / min / g)=(Flow rate (L / min)*(1m 3 / 1000L)*(Hg concentration*(μg / Nm 3 )*(1 / sample weight (g)) [Example]

[0080] Example 1 Four samples ("Samples 1-4") each initially comprised a sorbent polymer composite ("SPC") prepared using the general dry blending method taught in U.S. Patent No. 7,791,861 to form a composite sample, which was then uniaxially stretched according to the teachings of Gore's U.S. Patent No. 3,953,566 containing oxidized mercury and recovered after several years of field exposure to coal-fired power plant flue gas. The four samples of spent SPC were each in the form of a 10x150 mm piece, weighing approximately 1 gram each.

[0081] Samples 1-4, containing 50 parts activated carbon, 39 parts PTFE, and 6 parts halogen source in the form of TBAI, were treated with an aqueous solution containing 75 g / L potassium chloride. Potassium chloride was applied by spraying on both sides for Samples 1 and 2, dipping Sample 3 twice, and dipping Sample 4 for 30 minutes. Treated Samples 1-4 resulted in the conversion of treated SPC materials.

[0082] Samples 5 and 6 were in the form of 10x150mm pieces (approximately 1 gram each) of the same used SPC material described for Samples 1-4, and were obtained from the same field-exposed absorbent polymer composites described for Samples 1-4. The used SPC materials containing oxidized mercury were tested without treatment with potassium chloride solution; they were treated only by immersion in deionized water for 30 minutes.

[0083] A summary table of the treatments applied to each sample is provided below. [Table 1]

[0084] The samples were placed in a 10 mm x 10 mm square glass chamber in a 65°C oven. The samples were purged with air at a rate of approximately 10 standard liters per minute. The oxidized mercury vapor emission levels of the samples were measured using an RA915+ mercury analyzer (Ohio Lumex). The air was passed through a SnCl2 / H2SO4 bubbler before entering the mercury analyzer to convert the oxidized mercury to its elemental form for detection by the mercury analyzer. The emission rate was calculated using the following formula:

[0085] Release rate (μgHg / min / g)=(Flow rate (L / min)*(1m 3 / 1000L)*(Hg concentration*(μg / Nm 3 )*(1 / sample weight (g))

[0086] The results are shown below. [Table 2]

[0087] As shown, before treatment with the halogen source, all samples exhibited emissions greater than 0.01 μg Hg vapor / min / g SPC.

[0088] However, after treatment with a halogen source (potassium chloride solution), Samples 1-4 emitted less than 0.01 μg Hg vapor / min / g.

[0089] However, samples 5 and 6, which were not treated with potassium chloride solution but were immersed in deionized water, released 1.8–2.0 μg of oxidized mercury vapor per cubic meter of sample, a decrease in the average release of approximately 0.5 μg per cubic meter. The corresponding release rates from samples 5 and 6 were 0.018–0.020.

[0090] In summary, Example 1 shows that treatment of a spent adsorbent polymer composite material containing oxidized mercury with a halogen source (e.g., an alkali metal halide salt in the form of a potassium chloride solution) is clearly superior to treatment of the same adsorbent polymer composite material with deionized water.

[0091] Example 2 This example describes the mercury removal efficiency testing of two samples from Example 1 (ie, Samples 1 and 2).

[0092] Sample 1 from Example 1 was purged with air at a rate of approximately 10 standard liters per minute. The test temperature was 65°C. To measure the removal efficiency of Sample 1, mercury vapor was introduced using a heated permeation apparatus (VICI Metronics). The mercury vapor containing air was humidified to near saturation.

[0093] To measure mercury removal efficiency, an RA915+ mercury analyzer (Ohio Lumex) equipped with a short pathlength optical cell was used.

[0094] A 10% solution of tin(II) chloride in 10% sulfuric acid was used to treat the air effluent of Sample 1, ensuring that oxidized mercury was detected by the analyzer.

[0095] Sample 1 was tested for mercury removal efficiency.

[0096] Sample 1 was then sprayed on both sides with deionized water and retested for mercury removal efficiency.

[0097] Sample 1 was then treated on both sides with 5.5 ml of 1 molar potassium chloride solution and retested for mercury removal efficiency.

[0098] Sample 2 from Example 1 was treated on both sides with 5.5 ml of 75 g / L aqueous potassium chloride solution and tested for efficiency using the same procedure outlined above.

[0099] A summary table of the treatments applied to each sample is provided below. [Table 3]

[0100] The results of the efficiency measurements are shown below. [Table 4]

[0101] As shown, untreated Sample 1 exhibited a first mercury removal efficiency of 15.1%. When treated with deionized water, Sample 1 exhibited a mercury removal efficiency of 17.0%. In contrast, when treated with potassium chloride, Sample 1 exhibited a second mercury removal efficiency of 21.0%. Thus, the second mercury removal efficiency is approximately 45% higher than the first mercury removal efficiency.

[0102] Similarly, a second sample taken from the same material as Sample 1, Sample 2, showed a mercury removal efficiency of 23.0% after treatment with potassium chloride.

[0103] In summary, Example 2 shows that a used, exposed adsorbent-polymer composite containing oxidized mercury can be treated with a halogen source, potassium chloride solution (alkali metal halide salt), to achieve a mercury removal efficiency (second mercury removal efficiency) that is clearly higher than that of the untreated adsorbent-polymer composite (first mercury removal efficiency) and also higher than that of the adsorbent-polymer composite treated with deionized water.

[0104] Example 3 Five samples were cut from a sorbent polymer composite (SPC) prepared using the general dry blending method taught in U.S. Patent No. 7,791,861 to form composite samples, which were then uniaxially stretched according to the teachings of Gore U.S. Patent No. 3,953,566 and recovered after several years of field exposure to coal-fired power plant flue gas containing oxidized mercury from the process. Samples 1-5 were in the form of 10x150 mm pieces of used SPC material, each weighing approximately 1 gram.

[0105] Samples 1-5, containing 50 parts activated carbon, 39 parts PTFE, and 6 parts TBAI as a halogen source, were purged with air at a rate of approximately 10 standard liters per minute. The test temperature was 65°C. Mercury vapor was introduced via a heated permeation apparatus (VICI Metronics). The mercury vapor-laden air was humidified to near saturation.

[0106] To measure mercury removal efficiency, an RA915+ mercury analyzer (Ohio Lumex) equipped with a short pathlength optical cell was used.

[0107] A solution of 10% tin(II) chloride in 10% sulfuric acid was used to treat the sample air effluent, ensuring that oxidized mercury was detected by the analyzer.

[0108] Two samples (Samples 1-2) were tested for mercury removal efficiency without treatment.

[0109] Two of the samples (Samples 3-4) were immersed in an aqueous solution containing 10 ppm of NALSPERSE73551 surfactant manufactured by NALCO® and tested for mercury removal efficiency.

[0110] One of the samples (Sample 5) was treated with 10 ppm of the same surfactant. However, in Sample 5, 0.05 g of tetrabutylammonium iodide (TBAI) from Sigma Aldrich was added to the surfactant solution as a halogen source. Sample 5 was also tested for mercury removal efficiency.

[0111] A summary table of the treatments applied to each sample is provided below. [Table 5]

[0112] The removal efficiencies of the tested samples are shown in Figure 1 and in the table below. [Table 6]

[0113] As shown in the table above and in Figure 1, treatment of the spent sorbent-polymer composite with an aqueous solution of surfactant and a halogen source in the form of TBAI results in nearly three times higher mercury removal efficiency when compared to both (i) the untreated sorbent-polymer composite and (ii) the sorbent-polymer composite that was treated with an aqueous surfactant solution but not with a halogen source.

[0114] Example 4 The procedure outlined in Example 3 was repeated to prepare Samples 1-5 in the same way. However, rather than measuring mercury removal efficiency, the effect of the halogen source on mercury vapor release was measured. Release rates were assessed by simply subtracting the mercury vapor concentration 30 minutes into the test from the initial mercury vapor concentration at the start of the test.

[0115] The mercury vapor release rates for Samples 1 to 5 during the test period are shown below. [Table 7]

[0116] As shown, untreated Samples 1–2 exhibited a mercury release of approximately 0.05 μg Hg vapor / min / g SPC over the course of the test, indicating that the adsorbent-polymer composite became contaminated with oxidized mercury during the test, limiting the efficiency that could be achieved.

[0117] Similarly, Samples 3–4, which were treated with only the surfactant solution and no halogen source, exhibited release rates of approximately 0.03–0.05 μg Hg / min / g over the course of the test. This again indicates that in Samples 3–4, the adsorbent-polymer composite became contaminated with oxidized mercury during the test, limiting the achievable efficiency.

[0118] In sharp contrast, Sample 5, which was treated with a halogen source (e.g., TBAI) and surfactant, showed improved mercury efficiency over the 30-minute test. This indicates that for Sample 5, the sorbent-polymer composite became more effective at preventing mercury vapor release over time during the test, and performance was not limited by accidental release of oxidized mercury.

[0119] Example 5 Preparation of spent adsorbent polymer composites containing oxidized mercury A used sorbent-polymer composite was made under laboratory conditions containing 80 parts activated carbon and 20 parts PTFE ("sorbent-polymer composite"), prepared using the general dry-blending method taught in U.S. Pat. No. 7,791,861, and then uniaxially stretched according to the teachings of Gore, U.S. Pat. No. 3,953,566. A 5.5 gram sample of this was treated overnight with a 50 g solution of 0.1 g of HgI2 (Sigma-Aldrich) ("oxidized mercury"). The sample was allowed to air dry. A portion of the treated sample was analyzed by X-ray fluorescence ("XRF") and shown to have approximately 1 wt. % Hg.

[0120] Example 6 A 10 mm x 150 mm strip (0.79 g) was cut from the HgI2-treated sample from Example 5. The sample was placed in a 1 cm x 1 cm square sample holder at 60 °C. A stable baseline was established by bypassing the sample with 1 standard liter per minute of air humidified to greater than 80%. The effluent was passed through a SnCl2 / sulfuric acid trap cooled to 0 °C and then sent to a mercury analyzer (Ohio Lumex). The humid air was then sent through the sample. At this point, a very large mercury release (approximately 25,000 μg / m) was observed, as shown in Figure 2. 3 ) was observed. When the sample was again bypassed, the mercury level eventually returned to baseline. This large release of mercury was attributed to the vapor pressure of mercuric iodide above the sample.

[0121] The sample was removed from the holder and immersed in a halogen source of a 2 wt% solution of KI in methanol for 15 minutes. The sample was then air-dried and returned to the sample holder. No mercury release was detected when air was passed through the sample, indicating that treatment with potassium iodide effectively reduced mercury vapor release. Following testing, the sample was retested for HgI2 content by X-ray fluorescence (and found to contain approximately 1 wt% Hg, indicating that no significant amount of HgI2 was lost from the sample due to immersion). The sensitivity of this test, conducted at 1 slpm, is <0.0013 μg Hg vapor / min / g sample.

[0122] Example 7 A 10 mm x 150 mm strip (0.79 g) of the HgI2-treated sample from Example 5 was placed in a 1 cm x 1 cm square sample holder at 60 °C. A stable baseline was established by bypassing the sample with 1 slpm of air (humidified to >80%). The effluent was passed through a SnCl2 / sulfuric acid trap cooled to 0 °C and then sent to a mercury analyzer (Ohio Lumex). Humidified air was then sent through the sample. At this point, a very large mercury release (approximately 16,000 μg / m) was observed, as shown in Figure 3. 3 ) was observed. When the sample was again bypassed, the mercury level eventually returned to baseline. This large release of mercury was attributed to the vapor pressure of mercuric iodide above the sample.

[0123] The sample was removed from the holder and immersed in a 0.74 wt% solution of TBAI in methanol for 15 minutes, then air-dried and returned to the sample holder. No mercury release was detected when air was passed through the sample, indicating that treatment with TBAI effectively reduced mercury vapor release. Following testing, the sample was retested for HgI2 content by X-ray fluorescence and found to contain approximately 1 wt% Hg, indicating that no significant amount of HgI2 was lost from the sample due to immersion. The sensitivity of this test, performed at 1 slpm, is <0.0013 μg Hg vapor / min / g sample.

[0124] Example 8 Detection of mercury halide complexes in treated sorbent polymer composite (SPC) materials The formation of complexes with mercury halides occurs according to the following equations 1 and 2: HgX2+X - →HgX3 - (Formula 1) HgX3 - +X - →HgX4 2- (Formula 2) (wherein X is chloride (Cl - ), bromide (Br - ) and iodide (I - ) is).

[0125] The tendency to form complexes is - >Br - >Cl - increases in this order.

[0126] The reaction is generally independent of the cation that balances the charge of the complex anion, but the cation can affect the solubility of the complex. For example, compounds with complexed potassium cations, such as KHgI, can be soluble in water, while compounds with complexed tetrabutylammonium ([BuN]HgI), such as (BuN)HgI, can be soluble in water. + ) cation may be insoluble in water. In this specification and below, "Bu" refers to a butyl group.

[0127] XANES Overview XANES analysis is an abbreviation for X-ray absorption near edge spectroscopy. A sample is subjected to high energy X-rays (typically from a synchrotron). X-ray absorption is measured as a function of X-ray energy. The position and shape of the near edge absorption provides information about the oxidation state of the element. If appropriate standards are provided, the position and shape can also be used as a fingerprint to identify unknowns.

[0128] Synthesis of (Bu4N)HgI3 (1:1 complex) (Bu4N)HgI3 was synthesized to provide a standard for XANES studies.

[0129] 0.3716 g (1 mmol) of TBAI was dissolved in 75 mL of methanol. 0.4522 g (1 mmol) of HgI2 was added. The HgI2 dissolved within a few minutes, resulting in a pale yellow solution. The solution was stirred for 30 minutes. The solution was evaporated to dryness in a crystallizing dish. 0.69 grams of neon yellow needle-like crystals were obtained (Sample 1).

[0130] The synthesis was repeated using 0.3686 grams of TBAI and 0.454 grams of HgI2 in 75 mL of methanol. Upon evaporation, 0.75 grams of neon yellow crystals were recovered (Sample 2).

[0131] Elemental analysis of Samples 1 and 2 was performed by Galbraith Laboratories Inc.® of Knoxville, Tenn. The results are shown in Table 8 below.

[0132] [Table 8]

[0133] As shown, the elemental analysis results correlated with the theoretical values ​​for a 1:1 complex. Furthermore, the melting points obtained for Samples 1 and 2 correlated with literature values ​​obtained by Richard V. Snyder and Gerd N. La Mar, J. Am. Chem. Soc., 98(15), 4419-4424 (1976). For comparison, the melting points of TBAI and HgI2 are 141-143°C and 259°C, respectively. The correlations of both elemental analysis and melting points are taken as evidence that Samples 1 and 2 contained mercury halide complexes.

[0134] (TGA) (Bu4N)HgI3 vs. HgI2 and TBAI Volatility Reduction Thermogravimetric analysis was performed on HgI2 and Sample 1. Thermogravimetric analysis was performed using a TA Instruments TGAV5000 thermogravimetric analyzer by slowly increasing the sample temperature from ambient to 800°C while measuring mass loss in an air atmosphere using the TA Instruments Hi-Res dynamic method. The first derivative of mass loss with respect to time provides a measure of the temperature at which the maximum vaporization rate is reached. For HgI2, this peak was observed at 159°C. For (Bu4N)HgI3, the peak was at 258°C. From this analysis, it was clear that the mercury halide complexes in question were less volatile than HgI2.

[0135] XANES sample preparation Mercury compounds (HgI2 and (Bu4N)HgI3) used as reference samples were mixed with PTFE powder in a 1:1 ratio before being loaded into a Kapton tube.

[0136] Sorbent polymer composites ("SPC") containing oxidized mercury, as generally described in U.S. Pat. No. 9,827,551, were also recovered in the form of spent SPC samples after prolonged field exposure in the flue gases of a coal-fired power plant and drying at 120°C.

[0137] All samples were cut to a diameter of 1 mm and loaded into Kapton tubes using a wire. All samples were loaded into each Kapton tube until each tube contained 1-2 cm of each sample, and the ends were secured with modeling clay.

[0138] Experimental details of the XANES experiment XANES analysis was performed at the National Synchrotron Light Source at Brookhaven National Laboratory. Hg L 111 Edge X-ray spectra were obtained for both the reference sample and the field-exposed, used SPC sample. As noted above, the field-exposed, used SPC sample was obtained after prolonged exposure to flue gas from a coal-fired power plant. These samples had relatively low mercury content (due to the relatively low mercury concentration in the flue gas).

[0139] XANES graphs of HgI2 and (Bu4N)HgI3 Figure 4 shows the Hg L for HgI2, (Bu4N)HgI3, and field-exposed SPC samples. 111 The derivative of the XANES spectrum is shown.

[0140] Specifically, the field-exposed sample (see "XANES Sample Preparation") described above was a spent sorbent polymer composite (SPC) material prepared using the general dry blending method taught in U.S. Pat. No. 7,791,861 to form a composite sample that was then uniaxially stretched according to the teachings of Gore in U.S. Pat. No. 3,953,566. The field-exposed spent SPC sample contained 65 parts activated carbon, 20 parts PTFE, and 10 parts halogen source in the form of TBAI, and was exposed to the emissions of a commercial lignite coal-fired power plant for several months, containing approximately 0.2 wt.% Hg.

[0141] The HgI2 standard was reagent grade (>99%) HgI2 from Sigma Aldrich® (part number 221090).

[0142] The (Bu4N)HgI3 compound was prepared as described above.

[0143] Comparison of derivative spectra between the field-exposed samples and reference compounds (HgI2 and (Bu4N)HgI3) was used to determine the location and separation of inflection points in the spectra. The differences in the peaks and relative intensities of the field-exposed spent SPC samples compared to those of (Bu4N)HgI3 were attributed to the relatively low mercury concentrations in the flue gas used to treat the field-exposed spent SPC samples.

[0144] As shown in Figure 4, the peaks and relative intensities of the field-exposed spent SPC samples are closer to those of (Bu4N)HgI3 than to HgI2, indicating the possible presence of mercury halide complexes in the field-exposed spent SPC material.

[0145] While several embodiments of the present disclosure have been described, it is understood that these embodiments are illustrative only and not limiting, and that many variations may be apparent to those skilled in the art. For example, all dimensions discussed herein are provided by way of example only and are intended to be illustrative and not limiting.

Claims

1. adsorbent material, a polymeric material, and Chemical complexes containing oxidized mercury and a halogen source 1. An adsorbent polymer composite material comprising: the sorbent-polymer composite material releases less than 0.01 μg to 0.10 μg of oxidized mercury vapor per minute per gram when measured at 65° C. in air having 95% relative humidity; and The adsorbent-polymer composite material is characterized in that it comprises 0.1 wt % to 10 wt % of a halogen source based on the weight of the adsorbent-polymer composite material.

2. The chemical complex has the formula HgX 4 2- (wherein X is chloride (Cl - ), bromide (Br - ) or iodide (I - 10. The adsorbent polymer composite of claim 1, wherein

3. The chemical complex has the formula HgX 3 - (wherein X is chloride (Cl - ), bromide (Br - ) or iodide (I - 10. The adsorbent polymer composite of claim 1, wherein

4. The adsorbent-polymer composite material of any one of claims 1 to 3, wherein said chemical complex is integrated into the matrix of said adsorbent-polymer composite material.

Images